The work of adhesion at the interface of electrospun membrane and rigid substrate is measured by a shaft-loaded blister test (SLBT). Poly(vinylidene fluoride) (PVDF) were electrospun with an average fiber diameter of 333 ± 59 nm. Commercial cardboard with inorganic coating was used to provide a model substrate for adhesion tests. In SLBT, the elastic response PVDF was analyzed and its adhesion energy measured. The average value of the adhesion work is 206 ± 26 mJ/m2. Elastic modulus of electrospun membrane obtained by SLBT is found to be 23.42 ± 2.69 MPa, which is consistent with the value obtained from standard tensile tests. The results show SLBT presented a viable methodology for evaluating the adhesion energy of electrospun polymer fabrics.