Herein, we report the synthesis of a new supramolecular polymeric network (PCN) assembled through crosslinking of propyl bromide substituted tetraphenyl porphyrin with perhydroxy-cucurbit [8]uril and its use in the electrocatalytic hydrogen evaluation reaction after loading with nickel and integrating with in situ-electrochemically reduced graphene oxide (ERGO). Electrode was prepared by first coating graphene oxide on the FTO substrate followed by layering the nickel loaded PCN and finally by applying an appropriate voltage to reduce the graphene oxide in situ electrochemical reaction. The loading of nickel cocatalyst into PCN together with the integration of ERGO layer substantially improved its HER efficiency. Effect of various concentrations of Ni and GO on the HER activity of the developed electrocatalyst were investigated. Therein, ERGO1/Ni2@PCN catalyst containing 41% Ni and 50% GO (with respect to PCN) with only one layer of each component demonstrated excellent HER activity and stability with low onset and overpotentials of −20 mV, η@10 mA cm−2 of −360 mV, respectively, and remarkable hydrogen generation rate of 27.5 mmol h−1 g−1 in 1 M KOH. This noble-metal-free catalytic system is simple yet highly promising for the efficient hydrogen evolution reaction from water splitting.