In this work, the conductive composites of acrylonitrile‐butadiene rubber (NBR) and conductive carbon black (CCB) were prepared. The volume resistivity of NBR/CCB composites became stable when the addition content of CCB reached 12 wt %. However, when carbon fiber (CF) was added into the composites, the volume resistivity of NBR/CCB/CF composites continued to decrease with the increase of CF addition, which resulted from the formation of the three‐dimensional conductive network in composite matrix. In addition, the effect of acid oxidation of CF surface on the mechanical proprieties and conductive stability of NBR/CCB/CF composites was studied. The results indicated the acid oxidation of CF surface improved the bond structure between NBR and CF, which further decreased the resistance and significantly improved the mechanical properties of the composites. It was demonstrated that the conductive stability of NBR composites after cyclic mechanical and temperature fatigues was remarkably enhanced with the addition of CF. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46668.