alpha-Pinene and isobutene/isobutane can undergo hybrid alkylation under acid catalysis, resulting in C14 and C20 product fractions with favorable bio-based high-energy-density fuel properties after hydrogenation. In this study, the catalytic performance of zeolite molecular sieves, such as H beta, HY, HZSM-5, HZSM-35, HSAPO-11, was investigated for the alkylation of alpha-pinene and Isobut-5 (a mixture of isobutene/isobutane with a mass ratio of 1 : 5) given the acidic sites and specific pore structures with shape-selective abilities of zeolite catalysts. Various characterization techniques, including temperature-programmed desorption of ammonia (NH3-TPD), Fourier transform infrared spectroscopy with pyridine adsorption (Py-IR), N2 adsorption/desorption, X-ray fluorescence spectrum (XRF), and particle size analysis, were conducted to analyze the acidic properties, pore characteristics, silica-aluminum ratio, and grain size of the zeolites, and their influence on the alkylation of alpha-pinene and Isobut-5. Moreover, the recycling performance of the favorite H beta-25n catalyst and an effective regeneration method were investigated using temperature-programmed oxidation (TPO) analysis. This study provides essential research data for the preparation of alpha-pinene-based high-energy-density fuels. Hybrid alkylation performance of alpha-pinene with isobutene/isobutane towards bio-based high-energy-density fuels using H beta-25n zeolite as a catalyst.