The wear resistance of a Rh(111) surface can be strongly increased by interstitial alloying with boron atoms via chemical vapor deposition of trimethylborate [B(OCH3)3] at moderate temperatures of about 800 K. The fragmentation of the precursor results in single boron atoms that are incorporated in the fcc lattice of the substrate, as displayed by X-ray photoelectron diffraction. The penetration depth of the boron atoms is in the range of at least 100 nm with the boron distribution displaying a nearly homogeneous depth profile, as examined by combined X-ray photoelectron spectroscopy and Ar ion etching experiments. Compared to the bare Rh(111) surface, the wear resistance of the boron-doped Rh surface is increased to about 400%, as probed by the scratching experiments with atomic force microscopy. The presented synthesis route provides an easy method for case hardening of micro- or nanoelectromechanical devices (MEMS and NEMS, respectively) at moderate temperatures.