Abstract: This work demonstrates that MoOx/CeO2–ZrO2 solid acid acts as a promising catalyst in the solvent-free oxidative-coupling of benzylamine into dibenzylimine with O2 as the oxidant. The benzylamine conversions were found to be ~27, 51, 74, and 99 % for CeO2, CeO2–ZrO2, MoOx/CeO2, and MoOx/CeO2–ZrO2 catalysts, respectively. The MoOx/CeO2–ZrO2 catalyst also efficiently converts various substituted- and secondary-benzylamines under solvent-free conditions with O2 resulting in moderate to excellent yields. Remarkably, a high selectivity of ~99.6–99.9 % towards the dibenzylimine product was found for all reaction conditions. The outstanding performance of MoOx/CeO2–ZrO2 catalyst was attributed to high specific surface area, improved structural defects, and superior acid properties. Graphical Abstract: [Figure not available: see fulltext.] The MoOx/CeO2–ZrO2 catalyst show an outstanding performance in the oxidation of benzylamine and its derivatives, which is attributed to abundant acidic sites, large number of oxygen vacancies, and superior BET surface area. © 2015, Springer Science+Business Media Dordrecht.