Strategies to modify chromium nitride (CrN) surfaces are important because of the increasing applications of these materials in various areas such as hybrid electronics, medical implants, diffusion barrier layers, corrosion inhibition, and wettability control. The present work presents the first surface immobilization of alkyl and perfluoro-alkyl (from C6 to C18) chains onto CrN substrates using appropriately functionalized 1-alkynes, yielding covalently bound, high-density organic monolayers with excellent hydrophobic properties and a high degree of short-range order. The obtained monolayers were characterized in detail by water contact angle, X-ray photoelectron spectroscopy (XPS), ellipsometry, and infrared reflection absorption spectroscopy (IRRAS).