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Electrospun poly(vinylidene fluoride) (PVDF) nanofiber web has been widely utilized as a functional material in various flexible sensors and generators due to its high piezoelectricity,ease processability,and low cost.Among all the crystalline phases of PVDF,β-phase is a key property for PVDF nanofiber web,because the content of β-phase is directly proportional to piezoelectric performance of PVDF nanofiber web.Herein,the impact of graphene content (GC),tip-to-collector distance (TCD),and rotational speed of collector (RSC),as well as their interactions on the β-phase formation of PVDF nanofiber web is systematically investigated via design of experimental method.The fraction of each crystalline phase of PVDF nanofiber web is calculated by FTIR spectra,and the crystallinity is determined by XRD patterns.The influences of GC,TCD,and RSC on both β-phase fraction and crystallinity of PVDF nanofiber are analyzed using Minitab program.The results show that GC,TCD,and RSC all have significant effect on the β-phase content of PVDF nanofiber web,and GC is the most significant one.In addition,an optimal electrospinning condition (GC =1 wt％,TCD =4 cm,and RSC =2000 r·min-1) to fabricate highβ-phase crystallinity of PVDF nanofiber web is drawn,under which the crystallinity can reach 41.7％.The contributions in this study could provide guidance for future research on fabricating high performance PVDF nanofiber web based sensors or generators.