Polycaprolactone and polyvinyl alcohol are commonly used polymers with biocompatibility and biodegradability. However, the poor mechanical properties of polycaprolactone and the high swelling properties of polyvinyl alcohol hinder their application in guided tissue/bone regeneration. In this study, a new strategy for preparing absorbable guided bone regeneration (GBR) membrane was innovatively put forward, which was to simply blend them in formic acid in different proportions (0%/100%, 25%/75%, 50%/50%, 75%/25%, and 100%/0% wt/wt) and obtain nanofiber membrane by uniaxial electrospinning. The nano‐structure was confirmed by scanning electron microscope, and the change of chemical functional groups was confirmed by Fourier transform infrared spectroscopy. In addition, the proper polymer proportion (75%/25%) was selected through some tests. The results show that the nanofiber membrane has suitable wettability (104.083 ± 2.512°), sufficient Young's modulus (90.895 ± 7.431 MPa), the lowest swelling rate (33.705 ± 1.806%) and shrinkage rate (1.878 ± 3.252%), and no cytotoxicity. Its biodegradability and osteogenic effects in vitro were also investigated to show the potential applied in GBR.