Recently, low-dimensional organic-inorganic lead halide perovskites have attracted a great deal of attention due to their outstanding tunable broadband emission, while the toxicity of lead hinders their further application in the photoelectric field. Here, we report a novel lead-free Cu(I)-based organic-inorganic perovskite-related material of a (MA)4Cu2Br6 single crystal with zero-dimensional clusters, which is a unique Cu2Br64- corner-sharing tetrahedron dimer structure consisting of two connected tetrahedra. The single crystal displays a bright broadband green emission with a high photoluminescence with a quantum yield of ≤93%, a large Stokes shift, and a very long (microsecond) photoluminescence (PL) lifetime, resulting from self-trapped exciton emission. The direct band gap characteristic of (MA)4Cu2Br6 was proven by density functional theory calculation, and its band gap was determined by experiments to be ∼3.87 eV. In the temperature range of 98-258 K, the PL intensity increases gradually with an increase in temperature due to the deep trapping out of strong electro-phonon coupling, while the PL decreases when the temperature increases over 258 K due to phonon scattering. It is worth mentioning that this new material has high chemical and light stability, in contrast to the lead perovskite.