The use of non–precious metals for electrocatalytic hydrogen reaction (HER) is particularly important for energy conservation and environmental protection. In this work, three new cobalt corroles containing o−, m−, and p−nitrobenzyl (1, 2, 3) at the meso 10−position of the corrole macrocycle were synthesized, and their electrocatalytic hydrogen evolution reaction in organic and neutral aqueous systems was also investigated. The results show that these three cobalt corroles have significant catalytic HER activity in both systems, and the catalytic efficiency follows 1 > 3 > 2, which indicates that the position of the nitro group can affect the catalytic property of the complexes. In the organic phase, when using trifluoroacetic acid or p−toluenesulfonic acid as the proton source, the electrocatalytic HER may undergo an EECC (E: electron transfer, C: proton coupling) pathway. In a neutral aqueous system, the HER turnover frequency value of 1 is up to 137.4 h−1 at 938 mV overpotential.