Poly(vinylidene fluoride) (PVDF)/poly(methylmethacrylate) (PMMA) blend nanofibers were prepared by electrospray deposition (ESD). To control the diameter, morphology, and crystalline structure of nanofiber, the effects of the blending ratio and the humidity during ESD were investigated. The increase in the PVDF blending ratio reduced the average fiber diameter and enhanced formation of crystalline structure. In particular, ESD process enhanced crystal formation of PVDF in high-PVDF blending ratio. High humidity reduced the formation of beaded fiber and increased the average fiber diameter. These results provide fundamental information for preparation of the smooth and crystalline PVDF/PMMA blend nanofiber by ESD.