By the compound‐source molecular beam epitaxy (CS‐MBE), GaN:Eu and AlGaN films grown on both Al2O3(0001) and GaAs(100) substrates were prepared. Under RHEED observation, streak RHEED patterns from GaN were observed. This result shows that the surface of the film grown by CS‐MBE is atomically flat. From the XRD measurements, for GaN:Eu/Al2O3(0001), the film was oriented to c‐axis. On the other hands, for GaN:Eu/GaAs(100), the layer includes both the hexagonal and cubic phases. From the PL measurements, the PL spectra of both GaN:Eu/Al2O3 and GaN:Eu/GaAs(100) showed PL peaks related to Eu3+ ion. For GaN:Eu/GaAs(100), it is possible that part of Eu atom incorporates cubic‐GaN site (© 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)