Using hydrazine oxidation reaction (HzOR) to replace the oxygen evolution reaction is an effective way to decrease the overpotential of the anodic reaction in overall water splitting (OWS), facilitating cost‐effective and safe hydrogen production. Herein, Rh2S3/N‐doped carbon hybrids (Rh2S3/NC) are first reported as novel and efficient bifunctional electrocatalysts for hydrazine‐assisted hydrogen generation over a wide pH range. Specifically, Rh2S3/NC exhibits low overpotentials for the hydrogen evolution reaction (HER) in alkaline (38 mV), neutral (46 mV), and acidic (21 mV) electrolytes, to reach the current density of 10 mA cm−2, and maintains the activities over 70 h. Meanwhile, Rh2S3/NC also displays competitive HzOR performance at all‐pH electrolytes. Thus, serving as a bifunctional electrocatalyst for both HER and HzOR, Rh2S3/NC shows overwhelming‐Pt/C performance in three electrolytes, and can save over 93.3%, 85.2%, and 78.3% energy consumption compared to the corresponding OWS system. Moreover, theoretical calculations confirm that Rh2S3/NC owns low free‐energy changes of the H adsorption and the dehydrogenation of adsorbed NHNH both of which are beneficial to enhance catalytic activity. This work develops a novel bifunctional electrocatalyst with free pH‐dependent condition for the hydrazine‐assisted electrolysis system to furtherly reduce the cost of massive industrial H2 production.