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Electrospun fibre has shown great potential in tissue engineering and regenerative medicine due to its high specific surface area and extracellular matrix-mimicking structure. However, fabricating an electrospun fibrous scaffold with controllable complex 3D macroscopic configuration remains a challenge. In the present study, a novel method was designed to transform 2D electrospun poly (L-lactic acid) (PLLA) fibrous membrane to tubular PLLA fibrous scaffolds with 3D complex but tailored configuration. The electrospun PLLA fibrous membrane was rolled around a designed mould and then treated with acetone. Treated vascular grafts’ length, diameter, and shape can be tailored by the mould parameters. Moreover, treated vascular grafts achieve favourable mechanical properties (Young's modulus = 155 MPa, tensile stress = 8.79 MPa and radial force = 2.2 N) and the mechanical properties could be engineered on demand. In addition, treated vascular grafts kept their initial structure and size during long-term in vitro experiments once they were formed. In addition, with the acetone-induced recrystallization of PLLA, pristine solid PLLA fibres were changed to hierarchical porous PLLA fibres with ultra-high specific surface area (28.9 m2/g) and wettability (water contact angle = 101.32°), which has positive effects on cell adhesion and proliferation ability. A7r5 in vitro experiment shows that the proliferation rate of treated vascular grafts increased 153% at day 4 and 170.6% at day 7 compared with pristine vascular grafts.