Tunable multicolor luminescence materials can flexibly meet the needs of smart lighting, enabling efficient light energy use and minimizing waste. Lead-free hybrid double perovskites A2MIMIII(NO3)6 hold great potential in luminescence, benefiting from their tunable composition, high light absorption, low synthesis cost, and environmental friendliness. However, achieving tunable multicolor emission within a single matrix of these materials has yet to be realized. In this study, a series of [(CH3)4N]2KEu1–xTbx(NO3)6 single crystals have been synthesized using an environmentally friendly and mild aqueous solution evaporation method. The two emitter centers, Tb3+ and Eu3+, display energy transfer from Tb3+ to Eu3+. The emission color of the as-synthesized crystals gradually changes from red to orange, then to yellow, and finally to green with an increase of Tb3+ concentration, achieving yellow and green light emission in the three-dimensional rare-earth hybrid double perovskites for the first time. Green emission from [(CH3)4N]2KTb(NO3)6 displays the highest quantum yield at 87%. The millisecond-level emission decay time and high decomposition temperatures (365 °C) of [(CH3)4N]2KEu1–xTbx(NO3)6 single crystals highlight their potential for use in luminescent devices and phosphors, among other fields.