Ferromagnetism with perpendicular magnetic anisotropy (PMA) was observed at room temperature in cobalt nanoparticles (NPs) grown on hexagonal boron nitride (h-BN) on a Pt(111) surface. It was shown that the Co NPs have planar hexagonal shapes with a mean diameter of ∼20 nm and a mean height of ∼1.6 nm. The depth-resolved analysis of X-ray magnetic circular dichroism at the Co L2,3-edges revealed that in the ferromagnetic Co NPs, the ratio of the orbital magnetic moment to the spin magnetic moment in the out-of-plane direction becomes larger at the Co NP/h-BN interface than the ratio in bulk Co. The B and N K-edge near edge X-ray absorption fine structures showed the orbital hybridization between the π orbitals of h-BN and d orbitals of Co at the interface, as an origin of the orbital magnetic moment enhancement possibly giving rise to PMA in the Co NPs.