A hybrid Ni-based pseudocapacitive coating consisting of NiO–Ni3S4 on graphene petals is studied as an efficient electrode for supercapacitor applications. A single-source precursor of Ni is synthesized for coating on graphene petals supported on conducting carbon cloth as the current collector. The loading of Ni hexadecanethiolate on graphene petals surface is optimized with respect to electrochemical performance in terms of specific capacitance. The hybrid electrode gives high specific capacitance (≈2360 F g−1) and stability over 5000 cycles. Importantly, this coating process of Ni-based pseudocapacitive layer can be readily deployed in roll-to-roll (R2R) processes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim