On-surface Ullmann-type reaction, or the dehalogenated coupling, is arguably the most pivotal reaction in on-surface synthesis for the fabrications of carbon nanostructures. Hitherto, the vast majority of works rely on activating the C-Br bond of aryl bromide which has a moderate bonding dissociation energy. The C-Cl bond of aryl chloride has a larger dissociation energy and requires much higher thermal energy to break the bond. In this study, we have explored the on-surface photo-induced dechlorination and achieved the activation of three distinct aryl chlorines on the Au(111) surface with mild temperatures. This work enriches our understanding of on-surface photo-induced reactions and highlights the potential of photochemistry in realizing unconventional reactions.