A vinyl-terminated polycaprolactone has been developed for tissue engineering applications using a one-step synthesis and functionalization method based on ring opening polymerization (ROP) of ε-Caprolactone, with hydroxyl ethyl vinyl ether (HEVE) acting both as the initiator of ROP and as photo-curable functional group. The proposed method employs a catalyst based on aluminium, instead of the most popular Tin(II) 2-ethylhexanoate, to reduce the cytotoxicity. Following the synthesis of the vinylterminated polycaprolactone, its reaction with fumaryl chloride (FuCl) results in a divinyl-fumarate polycaprolactone (VPCLF). The polymers obtained were thoroughly characterized using Fourier transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC) techniques. The polymer has been successfully employed, in combination with N-vinyl pyrrolidone (NVP), to fabricate films and computer-designed porous scaffolds by micro-stereolithography (μ-SL) with gyroid and diamond architectures. Characterization of the networks indicated the influence of NVP content on the network properties. Human mesenchymal stem cells adhered and spread onto VPCLF/NVP networks showing good biological properties and no cytotoxic effect.