Abstract Hofmeister effect is a famous physical chemistry phenomenon that was reported a hundred years ago, which firstly refers to the action of certain salts to decrease the solubility of proteins while others increase. The Hofmeister effect on the luminescent properties of cationic organic fluorophore is still obscure, especially for their room temperature phosphorescence (RTP). Herein, hydrophilic groups (quaternization pyridine) were introduced into carbazole molecules to obtain a series of carbazole derivatives (named CZ‐Py+) with different counter anions in the Hofmeister series. These carbazole derivatives displayed tunable fluorescent color from cyan to yellow in the solid state following the Hofmeister sequence and anti‐Hofmeister behavior in an aqueous solution. Moreover, RTP material with tunable emission color and lifetime was achieved by doping CZ‐Py+ with Hofmeister series anion in polymethyl methacrylate and polyvinyl alcohol, which displayed good performance in time getting information encryption and anti‐counterfeiting.