Candida antarctica lipase B was successfully employed for the first time as a biocatalyst to obtain high molecular weight poly(butylene succinate-co-dilinoleic succinate) (PBS : DLS) copolyester via a two-stage method in a diphenyl ether solution from diethyl succinate, 1,4-butanediol, and dimer linoleic diol. The final hard to soft segments were close to the initial feed ratio as confirmed by H-1 NMR and FTIR measurements. Thermal analysis revealed the presence of two transitions typical for thermoplastic elastomers: a low temperature glass transition and high temperature melting point. In addition, the optimized synthetic protocol ensured high reaction yield (>74%) and molecular weight (M-w > 34 x 10(3) g mol(-1)) high enough to process the copolymer into electrospun mats without defects. The enzymatically synthesized PBS : DLS was able to be processed at 20-25 w/v% concentrations into fibres and depending on the type of solvent, the fibre diameter was controlled in the range of 0.3 to 0.6 mu m.