Purpose: The purpose of this study is to analyze intra-firm learning from previous alliance experience through the development and adoption of ad hoc organizational mechanisms. The investigated research question is: Do (and which kind of) alliance experience and deliberate learning mechanisms lead firms to alliance portfolio success? The aim of the paper is therefore to make a contribution towards the understanding of those organizational mechanisms leading to the generation and development of a firm-level collaborative know-how, i.e., the ability to manage each phase of interorganizational collaborations (Simonin, 1997). Design/Methodology/Approach: Focusing on the critical role that the management of strategic alliances plays for their success (Simonin, 1997; Anand and Khanna, 2000; Ireland et al., 2002; Kale et al., 2002), we use a three-dimensional theoretical framework in order to explore the relationship between collaborative experience (first dimension) and alliance portfolio performance (second dimension), as mediated through the adoption of organizational mechanisms (third dimension) for codification, abstraction, sharing and protection of the former in order to improve the latter. In particular, we evaluate whether alliance experience (and of which type) has a positive effect on alliance portfolio performance and whether such an effect is indeed mediated by the use of deliberate learning mechanisms. As to alliance experience, apart from the number of alliances, we look at its diversity in terms of governance structures and alliance goals. Following Heimeriks and Duysters (2007), we consider a 5-year period as an adequate temporal horizon reflecting the alliance contribution to firm's alliance experience. We use the performance of firms' alliance portfolios as dependent variable since we are interested in exploring the average impact of experience and organizational mechanisms on firms' alliance success. Indeed, firms' alliance capability by nature cannot be restricted to one alliance but it needs to be referred to the ability to manage effectively the entire alliance portfolio (Heimeriks and Duysters, 2007). As a consequence, our main concern is not whether a particular alliance is successful or not but rather whether the focal firm, using all of its alliances, is able to achieve the desired strategic goals (Hoffmann, 2005). Specifically, we evaluate alliance performance using managerial assessment (Geringer and Hebert, 1991; Kale and Singh, 2007) on different dimensions of alliance success: achievement of alliance objectives; enhancement of competitive position; learning of critical skills and capabilities; building of a strong relationship with alliance partners; contribution to firm image. Finally, several deliberate learning mechanisms are investigated: databases containing the firm's alliance history, manuals, checklists, formal and informal debriefings of alliance managers, alliance training systems, rotation across different partnerships of experienced alliance managers, alliance managers, dedicated alliance functions (Simonin, 1997; Kale et al., 2001, 2002; Zollo and Winter, 2002; Draulans et al., 2003; Heimeriks and Duysters, 2007; Kale and Singh, 2007). In line with Heimeriks and Duysters (2007), the abovementioned alliance mechanisms are measured by single-item dummy variables so that it could be possible to derive an index synthesizing firms' scores depending on the number of mechanisms in use. Moreover, we also look at when each mechanism was first used, excluding those recently activated since, by definition, they cannot contribute to alliance performance. Theory is tested through a quantitative analysis conducted on Campania Region aerospace firms. Indeed, the aerospace is a high-tech and innovation-based industry where alliances represent a fundamental element of firm strategy and success. A mail survey questionnaire was therefore sent to firms and assessed by managers responsible for the firm's alliances. Findings: Our study should contribute to shed light on the development of collaborative know-how, meant as the mixed effect of the extent and diversity of experience and its leverage through learning mechanisms, enabling firms to successfully manage interorganizational collaborations. Originality/Value: This study provides and validates a comprehensive framework for collaborative know-how, exploring the combined effect on alliance portfolio performance of several experience and learning dimensions, usually analyzed in isolation in previous research. Research limitations/implications: The study presents two main limitations. First, being tested on a single, specific industry, its results might not be fully generalizable. Second, the mere presence of some alliance mechanisms (such as databases, manuals, checklists, etc.) does not automatically imply their concrete adoption by firms. Therefore, it could be interesting for future research to verify if the framework is still workable when applied to firms operating in other industries and to investigate whether the presence of some learning mechanisms in firms really reflects their actual usage.