The organic-inorganic hybrid copper halides exhibit intriguing and complex photophysical properties, and the underlying mechanisms are far from clear. Here, we study the photodynamics of six novel types of low-dimensional hybrid copper halides, which have a maximum quantum yield of 98.6%. They exhibit two origins of photon emission with distinct temperature dependence and quantum transition rates. The experiments in junction with first-principles calculations indicate that they stem from two kinds of self-trapped excitons (STEs): one-center a-STE (localized on Cu+ monomer) and two-center m-STE (localized on Cu22+ dimer). There is phase transition between a-STE and m-STE when enough thermal energy is acquired for crossing the potential barrier between them. The degree of softness of the compositional organic cations of the copper halide plays a key role in determining the self-trapping type of the STEs.