Both pH-sensitive and glucose-responsive rhodium oxide nanocorals (Rh2O3 NCs) were synthesized through electrospinning followed by high-temperature calcination. The as-prepared Rh2O3 NCs were systematically characterized using various advanced techniques including scanning electron microscopy, X-ray powder diffraction and Raman spectroscopy, and then employed as a dual functional nanomaterial to fabricate a dual sensor for both non-enzymatic glucose sensing and solid-state pH monitoring. The sensing performance of the Rh2O3 NCs based dual sensor toward pH and glucose was evaluated using open circuit potential, cyclic voltammetry and amperometric techniques, respectively. The results show that the as-prepared Rh2O3 NCs not only maintain accurate and reversible pH sensitivity of Rh2O3, but also demonstrate a good electrocatalytic activity toward glucose oxidation in alkaline medium with a sensitivity of 11.46 μA·mM·cm−2, a limit of detection of 3.1 μM (S/N=3), and a reasonable selectivity against various interferents in non-enzymatic glucose detection. Its accuracy in determining glucose in human serum samples was further demonstrated. These features indicate that the as-prepared Rh2O3 NCs hold great promise as a dual-functional sensing material in the development of a high-performance sensor for both solid-state pH and non-enzymatic glucose sensing.