The production of Fischer-Tropsch liquid biofuels from the supercritical water gasification (SCWG) of lignocellulosic biomass is energetically and environmentally assessed by coupling process modelling with Life-Cycle Assessment. A conceptual process model has been developed comprising the following stages: (a) the thermochemical conversion of lignocellulosic biomass in a supercritical water gasification (SCWG) reactor, (b) syngas upgrade through dry reforming (DRR), (c) liquid biofuel production from Fischer-Tropsch synthesis (FTS) and (d) FT product upgrade and refinement, so that diesel-like (FT-Diesel), gasoline-like (FT-Gasoline), and jet fuel-like (FT Jet Fuel) yields are predicted. Parametric studies have been performed, highlighting the effect of biomass concentration and SCWG temperature on end-product yields. Furthermore, alternative scenarios have been examined with respect to: (a) maximizing FT liquid biofuel yields and (b) minimizing heat requirements to potentially achieve a thermally self-sustained process. The results of the simulated process, including liquid biofuel yield and heat-demand predictions, are used as inputs in the inventories compiled for the Life-Cycle Assessment of the overall process. Agricultural and feedstock transportation stages have also been considered. Energetic and environmental benefits and challenges are highlighted through the quantification of Global Warming Potential (GWP), while special importance is assigned to following the REDII sustainability methodology and reference data.