Precipitation hardened nickel-based Alloy 725 (UNS N07725) has been proven susceptible to hydrogen embrittlement in oil and gas production. Moreover, current standards cannot differentiate unequivocally between acceptable and affected microstructures, making the development of an appropriate quality control test a priority for the oil and gas industry. Recently, Alloy 725 failures were associated with the precipitation of nanoscale Cr- and Mo-rich phases at grain boundaries (GBs). Since these intergranular precipitates could lead to Cr- and Mo-depletion along the decorated GBs (i.e., sensitization), the double-loop electrochemical potentiokinetic reactivation (DL-EPR) test was explored as an alternative approach to detect affected microstructures. Herein, the DL-EPR technique was optimized for Alloy 725 by testing three types of samples with different degrees of sensitization, including a full GB-decorated microstructure that was shown prone to hydrogen embrittlement in oil and gas service. The optimized DL-EPR test conditions were 2 M HCl + 1 M H2SO4 + 10−4 M KSCN aqueous solution at 30 °C with a 1.667 mV s−1 scan rate and a vertex potential of Ecorr + 700 mV. Results were reproducible and consistent with the degree of GB decoration determined using metallographic methods. The test procedure developed herein could lead to the standardization of the DL-EPR method for Alloy 725.