The substrate-surfaces treated with carboxylatochromium complexes are shown to produce homeotropic molecular alignments of three different kinds of liquid crystals, i.e., nematic (MBBA), smectic (BBBA), and largepitch cholesteric (l wt.% CC in MBBA) fluids. The complexes used are tetrachloro-μ-hydroxo-μ-carboxylatodichromium (III) having myristato and perfluorononanoato as the carboxylato ligand, respectively. The orientation effect of the complexes on liquid crystals is briefly discussed.