In one aspect, articles are described herein comprising refractory coatings employing alumina-based hybrid nanocomposite architectures. A coated article described herein comprises a substrate and a coating deposited by CVD adhered to the substrate, the coating including a composite refractory layer having a matrix phase comprising alumina and at least one particulate phase within the matrix phase, the particulate phase comprising nanoscale to submicron particles formed of at least one of an oxycarbide and oxycarbonitride of one or more metals selected from the group consisting of aluminum and Group IVB metals.