Complexes of Sc, La, Sm, Gd, Tb and Yb with 1,3‐di‐tert‐butyl‐7‐methylacridin‐4‐olate (AcrMe) and 1,3‐di‐tert‐butyl‐7‐bromoacridin‐4‐olate (AcrBr) ligands were obtained by reactions of respective acridinols with cyclopentadienides or tris(trimethylsilyl)amides of rare earth metals or by metathesis of metal chlorides with Na(AcrR). The Sc and La complexes with AcrMe ligands revealed photo‐ and electroluminescence of moderate intensity while the Sm, Gd, and Tb complexes, as well as all complexes with AkrBr ligands, turned out to be luminescent inactive. The La(AkrBr)3 and Yb(AcrBr)3 complexes showed photovoltaic properties. The best results of energy conversion were achieved on three‐layer model devices containing a lanthanum complex as a photoactive material.