Abstract Using metal–organic (MO)CVD, lanthanum trifluoride (LaF3) and oxyfluoride (LaOF) films are deposited on Si(100), glass, and quartz from a La(hfa)3diglyme single‐source precursor. The films are characterized using X‐ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AFM). They are found to be crystalline with a high degree of fiber texture even when deposited on glass or quartz substrates. The SEM indicates very homogeneous surfaces with grain dimensions decreasing upon increasing the deposition temperature and the oxygen flow. The AFM data indicate a very smooth surface with a root mean square (rms) roughness of 0.96 nm for films deposited at high temperature/high oxygen flow.