Poly(vinyl alcohol)/collagen (PVA/COL) micro-nanofibers were successfully prepared by electrospinning process. Water, green, and non-toxic was used as the solvent. The electrospun mats consisted of micro-nanoscale fibers with mean diameter ranging from approximately 363 nm to 179 nm. It was observed that the mean diameters of PVA/COL electrospun fibers decreased with increasing collagen content. The effects of PVA/COL blending ratio on the rheological behavior of PVA/COL blended solutions were investigated by rotate rheometer. It was found that PVA/COL blended solutions behaved as Non-Newtonian fluids. With increasing collagen content, the Non-Newtonian index (n) of PVA/COL blended solutions decreased. Meanwhile, a linear relationship was found between the Non-Newtonian index (n) and the mean diameters of the PVA/COL micro-nanofibers. The chemical structures of PVA/COL electrospun fibers were also characterized by FTIR.