In this study, poly(amic acid) was prepared via a polycondensation reaction of 3,3’-dihydroxybenzidine and pyromellitic dianhydride in an N-methyl-2-pyrrolidone solution; reduced graphene oxide/polybenzoxazole (r-GO/PBO) composite films, which significantly increased the electrical conductivity, were successfully fabricated. GO was prepared from graphite using Brodie’s method. The GO was used as nanofillers for the preparation of r-GO/PBO composites through an in situ polymerization. The addition of 50 wt% GO led to a significant increase in the electrical conductivity of the composite films by more than sixteen orders of magnitude compared with that of pure PBO films as a result of the electrical percolation networks in the r-GO during the thermal treatment at various temperatures within the films.