An efficient molybdenum‑niobium-oxide nanomaterial was synthesized by a one-pot hydrothermal method for selective C-O (glycerol ketalization) and C-N coupling (benzylamine oxidation) reactions. The catalytically favourable properties, such as defective metal sites, truncated surfaces, and uniform metal dispersion in the MoO3-Nb2O5 nanorods, calcined at 500 °C (MoNb OPS-5), were confirmed by Raman, HR-TEM, and STEM-EDX, respectively. Because of improved Lewis/Brønsted acidic strength, the MoNb OPS-5 catalyst showed higher activity in glycerol ketalization and benzylamine oxidation at mild conditions, giving superior selectivity to solketal (97%) and dibenzylimine (99%), respectively. The MoNb OPS-5 catalyst showed high structural stability and considerable good reusability efficacy.