Herein, we report a novel hybrid organic-inorganic Zr(IV) metal halide ((CH3)4N)2ZrCl6, which demonstrates fascinating excitation-dependent luminescence across the full visible region. The single crystal of ((CH3)4N)2ZrCl6 showed an unexpected high degree of symmetry and formed a unique 0D structure with isolated [ZrCl6]2- octahedrons. Amazingly, three different emission groups emerged under changeable excitation light. The first emission group peaked at 462 nm with a ns lifetime and a μs lifetime, which is assigned to free-exciton fluorescence and thermally activated delayed fluorescence (TADF). The second group of emissions featured elaborate multipeak light-emitting components, which is ascribed to the d-d transitions of Zr(IV). The third emission group centered at 660 nm was attributed to the typical self-trapped exciton (STE) emission. To our best knowledge, this work for the first time reports a 0D organic-inorganic metal halide with distinctive excitation-dependent full-visible-spectrum luminescence via four different emission mechanisms.