The unique luminescent properties of mechanoluminescence (ML) have demonstrated immense potential for applications in fields such as mechanical sensing, anti-counterfeiting, and display imaging. In this work, a series of multicolor luminescent Ca_0.95-xZnOS: 0.05Bi³⁺, xEu³⁺ (x = 0–0.04) were synthesized through the high-temperature solid-state reaction method. An energy transfer (ET) process from Bi³⁺ to Eu³⁺ was observed when Eu³⁺ was introduced. The introduction of Eu³⁺ led to an observed energy transfer process from Bi³⁺ to Eu³⁺. The photoluminescence (PL) color shifted from blue-green to red, and the afterglow (AG) shifted from blue to red as the concentration of Eu³⁺ increased. Furthermore, CaZnOS: Bi³⁺, Eu³⁺ exhibits red ML with the highest intensity of 3% Eu³⁺ concentration, which is 14% higher than CaZnOS: 0.05Bi³⁺. The ML intensity exhibits a linear correlation with the stress level and can be applied to stress sensing. Therefore, a light-emitting device composed of CaZnOS: Bi³⁺, Eu³⁺ and PDMS possesses three light-emitting modes: PL, AG, and ML, which is suitable for optical anti-counterfeiting.