This study aims to examine the adhesion work of electrospun polymer nano- and micro-fibers. The adhesion energy at the interface of electrospun membrane and a rigid substrate is characterized by a shaft-loaded blister test (SLBT). By controlling the processing parameters, polyvinylidene fluoride (PVDF) fibrous membranes are prepared with fiber diameters ranging from 201 ± 86 nm to 2,724 ± 587 nm. The adhesion energy between electrospun membrane and rigid substrate increases from 8.1 ± 0.7 mJ/m2 to 258.8 ± 43.5 mJ/m2 by use of smaller fiber diameters. Adhesion energies between electrospun PVDF membranes and SiC substrates made of different grain sizes are evaluated. Fibrous membrane produces an adhesion energy as high as 420.1 ± 62.9 mJ/m2 in contact with SiC substrate with a 68 μm grit size. The SLBT methodology is extended to understand the adhesion energy between electrospun membranes. The increase in adhesion work is attributed to an increased area between fiber delaminated surfaces and surface asperities
