Formation window of layered La2(OH)4SO4·nH2O was defined.
Oxysulfate and oxysulfide were facilely derived from the layered compound.
Crystal structures of La2(OH)4SO4·nH2O, oxysulfate and oxysulfide were deciphered.
Multi-color photoluminescence was achieved in oxysulfate and oxysulfide.
Concentration and host dependent luminescence was well addressed.