Poly(L-lactide) (PLLA) and PLLA/poly(trimethylene carbonate) (PTMC) scaffolds characterised by different PLLA:PTMC mass ratios (10:0, 9:1, 8:2, 7:3, 6:4 and 5:5) were prepared via electrospinning. The results showed that increasing the PTMC content in the spinning solution caused the following effects: (1) the diameter of the prepared PLLA/PTMC electrospun fibres gradually increased from 188.12 ± 48.87 nm (10:0) to 584.01 ± 60.68 nm (5:5), (2) electrospun fibres with uniform diameters and no beads could be prepared at the PTMC contents of >30%, (3) the elastic modulus of the fibre initially increased and then decreased, reaching a maximum value of 74.49 ± 8.22 Mpa (5:5) and (4) the elongation at the breaking point of the fibres increased gradually from 24.71% to 344.85%. Compared with the PLLA electrospun fibrous membrane, the prepared PLLA/PTMC electrospun fibrous membrane exhibited considerably improved mechanical properties while maintaining good histocompatibility.