The magnetic coupling interaction of Mn2+-Mn2+ in Mn2+-included phosphors could induce a shorter emission decay time, compared with that of isolated Mn2+, which could overcome the photoluminescence (PL) saturation when stimulated by a high photon flux due to the long lifetime of the Mn2+ excited state. However, few studies have directly proved the Mn2+-Mn2+ coupling effect on the PL decay. In this paper, the effect on PL of CsMnCl3 (CMC) and its hydrates is revealed by photomagnetism results, excluding the interference effects of site symmetry and phonon energy. The antiferromagnetic interaction of the CMC is larger when Mn2+ at a photoexcited state than at a dark state, which is contrary to the hydrates with weak Mn2+-Mn2+ interaction. This research not only helps researchers to understand the fundamental optical process but also is instructive for designing high performance Mn2+-doped phosphors in the field of displays and lighting.