Novel structural and chemical properties of Cr monolayer, bilayer, and multilayer films on W(110) have been identified using temperature programmed desorption, low-energy electron diffraction, and Auger electron spectroscopy. A pseudomorphic (1×1) Cr monolayer forms at T>100 K which is stable up to desorption at ∼1290 K despite a ∼9% lattice mismatch. The second monolayer forms a metastable (2×2) structure in the 500 K <T<800 K range, for which a quad-cluster model is proposed. An (11×11) coincidence lattice is observed for multilayer films. Oxidation of the Cr overlayers leads to both an interfacial oxide and Cr2O3-like phases. Cr2O3/W(110) incommensurate epitaxy is observed for thick Cr films.