Flexible sheets consisting of acrylonitrile–butadiene rubber (NBR) and vapor-grown carbon fiber (VGCF) are newly prepared varying the composition (VGCF 10–30 wt%) for use as a current collector of supercapacitor electrodes. The electrical conductivity of as-prepared VGCF/NBR current collector can be enhanced as the content of VGCF increases. The VGCF/NBR current collector is then electrodeposited with pyrrole using a potentiodynamic cyclic voltammetry to yield a polypyrrole (PPy)/VGCF/NBR composite electrode. Cyclic voltammetry result for the PPy/VGCF/NBR composites shows that the sample with 30 wt% VGCF achieves a maximum specific capacitance (125.8 F g⁻¹) at 5 mV s⁻¹ and reaches a lower specific capacitance at higher scan rates. In addition, the flexibility of supercapacitor electrode of PPy can also be established with a comparable capacitance value by using the NBR-based current collector.