Abstract Achieving on‐demand control of responsive behaviors of photochromic molecules is important for advanced photonic applications, but it remains a challenge. In this work, a triphenylethylene‐based molecule, 5‐(2,2‐bis(4‐fluorophenyl)vinyl)‐5″‐methyl‐2,2″‐bipyridine ( 1 ), which can undergo open‐to‐closed isomerization under 365 nm irradiation, is designed and synthesized. Importantly, on‐demand acceleration or deceleration of photoisomerization rate over a wide range ( k UV = 0.00584–0.06299 s −1 ) is achieved by coordination of 1 with different metal salts. Furthermore, more precise manipulation of the photoisomerization rate is achieved by changing the counterions of the 1 ‐based metal complex. Eventually, taking advantage of distinctly different photoisomerization rates of 1 and its corresponding metal complexes, high‐level irradiation time‐dependent information encryption and anticounterfeiting applications have been demonstrated.