In this study, we presented the use of polyurethane, ethylene-vinyl acetate hotmelt, and nano hexagonal boron nitride particles to prepare high surface adhesion polymer fibers via an elertrospinning method. The shear strength, dynamic tensile properties, and surface morphology have been investigated. These polymer fibers were found to have high shear strength, high tensile stress, and high tensile strain, which may have a good potential application in the matrix materials for thermal interface materials. Polymer fibers with and without nano hexagonal boron nitride particles showed the shear strength of 6.52 MPa and 5.44 MPa respectively on being heated up at 150°C for 45 min.