Rising electricity demand and growing concerns over climate change underscore the urgent need for efficient and low‐carbon power generation technologies. In this context, selecting the suitable fuel cell technology becomes critical to achieving both high technical performance and environmental sustainability. This study presents a comprehensive model for two different hybrid power generation systems: one comprising a hydrogen‐fueled proton exchange membrane fuel cell (PEMFC) with an Organic Rankine Cycle (ORC) heat recovery system, and the other comprising a direct methanol fuel cell (DMFC) with ORC. A comparative assessment is conducted to investigate and compare the energetic, exergetic, economic, and environmental (4E) performance of these systems as a function of current density. Both systems are designed to produce the same peak electrical output (≈70 kW), allowing for a meaningful comparison. The 4E analysis reveals that PEMFC‐ORC achieves greater energy efficiency (35% vs. 29%), while DMFC‐ORC demonstrates superior exergy performance (55% vs. 42%) and a more favorable levelized cost of electricity ($0.27/kWh vs. $0.63/kWh). Nonetheless, DMFC‐ORC incurs a significantly higher environmental burden, with annual CO2‐equivalent emissions nearly twice those of PEMFC‐ORC. These identified trade‐offs inform tech- nology choices that align with the interconnected objectives of Sustainable Development Goal 7 (Affordable and Clean Energy) and Sustainable Development Goal 13 (Climate Action).

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