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The objective of this work is to propose an integrated system for formic acid synthesis via photovoltaic (PV) assisted‐chloralkali process and clean power generation by the fuel cell. The initial step is to develop process flow diagrams and to apply heat integration techniques to conserve energy in the synthesis of formic acid and direct formic acid fuel cell (DFAFC). The proposed system forms formic acid from gaseous H2 produced from chloralkali unit and captured CO2. The electricity requirements of both PV‐assisted chloralkali and compression stages are supplied from the PV units. The results imply that the chloralkali process necessitates about 7.22 MW power to produce hydrogen at 25°C and 1 bar with an energy efficiency of 84%. H2 and CO2 gases are compressed to 60 bars with a total energy requirement of 951 kW. In the heat integration part, different scenarios are developed to determine the minimum heating and cooling requirements for maximum heat recovery. The results of such heat integration were achieved to conserve the energy in the formic acid process with total hot and cold utilities of 599 kW and 1884 kW, respectively.