It is highly attractive to construct a natural enzyme-free electrode for sensitive and selective detection of glucose. In this Letter, we report that a Ni2P nanoarray on conductive carbon cloth (Ni2P NA/CC) behaves as an efficient three-dimensional catalyst electrode for glucose electrooxidation under alkaline conditions. Electrochemical measurements demonstrate that the Ni2P NA/CC, when used as a nonenzymatic glucose sensor, offers superior analytical performances with a short response time of 5 s, a wide detection range of 1 μM to 3 mM, a low detection limit of 0.18 μM (S/N = 3), a response sensitivity of 7792 μA mM–1 cm–2, and satisfactory selectivity, specificity, and reproducibility. Moreover, it can also be used for glucose detection in human blood serum, promising its application toward determination of glucose in real samples.