An effective non-noble-metal electrocatalyst for alkaline water electrolysis must enable fast electron transfer, high reactivity at the surface-liquid interface, stable active-site chemistry, and minimal current leakage upon prolonged bias application. Alkaline hydrogen evolution catalysts based on Co–N–C materials derived from ZIF-67 precursors are appropriate choices in this regard owing to the ability of their cobalt-imidazolate chemistry to tune metal centers, nitrogen incorporation, and conductive porosity of the carbon matrix simultaneously. In this work, we analyze the electrochemical properties of a series of sequentially chemically linked ZIF-67 (unchanged), ZIF-67@DCD (dicyandiamide), and NiSAs@ACNTF (nickel addition) catalysts. Combination of LSV, CV, and CA analyses allows for differentiation between real improvements of catalytic kinetics and alterations of double-layer capacitative properties. The latter show a decreasing trend in the CV-based sequence: ZIF-67 (7.28 mF cm−2) > ZIF-67@DCD (5.14 mF cm−2) > NiSAs@ACNTF (4.89 mF cm−2). However, the LSV profile selects NiSAs@ACNTF as the best-performing candidate. Thus, higher catalytic activity of the catalyst with nickel addition cannot be accounted for by the growth of its capacitive interface, and should rather be attributed to better active site chemistry and increased electronic interaction within the nitrogen-doped carbon host. CA data reveal the stability of the activity edge during a ten-hour operating regime after the initial activation process. The key finding of the work lies in a combined analysis of kinetic, capacitive, and durability parameters that characterize accessible surface, catalytic performance, kinetic rate, and retention within a precursor family.