Herein, we propose a facile strategy to prepare hierarchical flower-like MoO2@ N, P co-doped carbon (NPC) hybrids on flexible carbon cloth (CC) as a self-standing and binder-free anode for sodium ion batteries. The construction of hierarchical MoO2 nanoflowers and the formation of NPC can be synchronously achieved via one-step pyrolysis of molybdophosphate-based ionic liquid precursor on CC. Serving as anode material for sodium ion batteries, the as-prepared CC@NPC@MoO2 electrode exhibits a high reversible capacity (821 mA h g−1 after 100 cycles at 100 mA g−1), excellent rate capability and cycling stability (321 mA h g−1 at 1 A g−1 after 600 cycles). The excellent electrochemical performance can be attributed to the uniquely hierarchical flower-like structure, which can effectively shorten the ion diffusion paths and promote the rapid ion insertion/extraction, thus boosting the sodium storage capacity. Moreover, the in-situ formed NPC on flexible CC is able to improve the charge transfer efficiency and maintain the structural integrity even after long-term cycles.