The Poly (vinyl alcohol)/Potassium hydroxide (PVA/ KOH) nanofiber Composites for application as a supercapacitor electrolyte. Electrospinning method has been successfully used to synthesize composite of the PVA/KOH nanofiber. The PVA and KOH have been made with concentration are 5% w/w (PK1), 10% w/w (PK2) and 15% w/w (PK3), with a mass ratio of PVA/KOH is 10:1. The Physicochemical properties of PVA/KOH nanofibers with three various in the experiment were studied, including morphology, size, and chemical interaction. The microscope result shows that nanofiber of PK1, PK2 and PK3 have bead fiber and free- bead fiber, Where the PK1 is bead fiber and the PK2 and PK3 are free-bead fiber. The average diameter of PK1, PK2 and PK3 were 635, 826, 1021 nm, respectively. The FTIR results show that there is interaction between Poly (vinyl alcohol) and Potassium hydroxide (KOH) in the form of a spectrum and widening of transmittance are 3320 cm(-1) and 3301cm(-1) which identifies hydrogen bonds.