While spatial and time-resolved anti-counterfeiting technologies have gained increasing attention owing to their excellent tunable photoluminescence, achieving high-security-level anti-counterfeiting remains a challenge. Herein, we developed a spatial-time-dual-resolved anti-counterfeiting system using zero-dimensional (0D) organic–inorganic Mn(II) metal halides: (EMMZ)2MnBr4 (named M−1, EMMZ=1-Ethyl-3-Methylimidazolium Bromide) and (EDMMZ)2MnBr4 (named M−2, EDMMZ=1-Ethyl-2,3-Dimethylimidazolium Bromide). M−1 shows a bright green emission with a quantum yield of 78 %. It undergoes a phase transformation from the crystalline to molten state with phosphorescence quenching at 350 K. Reversible phase and luminescent conversion was observed after cooling down for 15 s. Notably, M−2 exhibits green light emission similar to M−1 but undergoes phase conversion and phosphorescence quenching at 390 K, with reversible conversion observed after cooling down for 5 s. The photoluminescence switching mode of on(green)-off–on(green) can be achieved by temperature control, demonstrating excellent performance with short response times and ultra-high cyclic reversibility. By leveraging the different quenching temperatures and reversible PL conversion times of M−1 and M−2, we propose a spatial-time-dual-resolved photoluminescence (PL) switching system that combines M−1 and M−2. This system enables multi-fold tuning of the PL switch for encryption and decryption through cationic engineering strategies by modulating temperature and cooling time. This work presents a novel and feasible design strategy for advanced-level anti-counterfeiting technology based on a spatial-time-dual-resolved system.