A new method for the synthesis of layered europium basic chloride in up to 90% yield was developed. The method is based on hydrolysis of europium chloride in the presence of propylene oxide. The effect of reaction temperature on the yield and composition of the products of europium chloride hydrolysis in the presence of propylene oxide was analyzed. The obtained layered europium basic chloride had pronounced anion exchange properties. The possibility of intercalation of the isonicotinate anion into a layered rare earth hydroxide was demonstrated for the first time. The intercalation of the benzoate or isonicotinate anions into layered europium hydroxide led to luminescence sensitization and decrease in the Eu3+ local symmetry.