In this paper, a new zero-dimensional organic-inorganic hybrid manganese bromide single crystal with high-efficiency yellow-green emission has been synthesized by inserting C₆H₁₆N₂²⁺ into [MnBr₄]^2- tetrahedrons lattice, and its PLQY reaches up to 89%. At the same time, the relationship between the emission wavelength and relaxation process under CW laser excitation was investigated in this single crystal, exhibiting different emission colors under continuous-wave laser excitation of different wavelengths. The results show that the distance between the nearest Mn²⁺ in the lattice is 6.8 Å, this number brings up a very weak ferromagnetic coupling state and a dominant paramagnetic state, which lead to a significant emission band at 550 nm and a weak emission band at about 640 nm when excited by 325 nm laser. The high-level d-d transition at about 400 nm and AFM d-d transition at 458 nm band could be found simultaneously under continuous-wave laser excitation above the bandgap, and the photophysical properties of the multiple emission bands and the microscopic interactions of the spin, carrier, and phonon inside the lattice have been discussed. These findings provide a new direction for Mn-based materials in the field of luminescence and provide ideas for the development of new materials with the microscopic interaction modulation of the spin, carrier, and phonon.