Photoredox catalysis has emerged as an alternative to classical cross-coupling reactions, promoting new reactivities. Recently, the use of widely abundant alcohols and aryl bromides as coupling reagents was demonstrated to promote efficient coupling through the Ir/Ni dual photoredox catalytic cycle. However, the mechanism underlying this transformation is still unexplored, and here we report a comprehensive computational study of the catalytic cycle. We have shown that nickel catalysts can promote this reactivity very efficiently through DFT calculations. Two different mechanistic scenarios were explored, suggesting that two catalytic cycles operate simultaneously depending on the concentration of the alkyl radical.