Polyaniline nanofiber (PANF) was synthesized using interfacial polymerization and was mixed with aqueous solution of poly(vinyl alcohol) (PVA) to form PANF–PVA binaries. The PANF suspension in water could be stabilized by PVA for more than 3 months due to the hydrogen bonding interaction between PANF and PVA. The specific characteristics of PANF–PVA films was checked by scanning electron microscopy, conductivity measurement, thermogravimetric analysis, Fourier transform infrared spectroscopy, and cyclic voltammetry. The composite film contained 25 wt% PVA (PANF–PVA25) casting at 105 °C was found to have a porous structure and good conductivity. The presence of hydrogen bonding interaction between PANF and PVA improves the electroactivity and electroactive stability of PANF–PVA25 for electrochemical applications. However, an ether linkage between PANF and PVA polymer chain was also found as casting the PANF–PVA film at 200 °C, which is unfavorable for electrochemical applications.