The three dimensional hierarchical carbon microflowers decorated with MoO2 nanoparticles (MoO2/CF) were fabricated by a facile method. During the experiment process, MoO4 2− anions are attached on the dopamine along with self-polymerization of dopamine under alkaline solution, forming the Mo-polydopamine compound (AHM-PDA). Then it is carbonized, forming MoO2/CF. The size of the MoO2/CF can be adjusted by the amount of dopamine, and the MoO2 nanoparticles decorated on the carbon microflowers are 1–2 or 30–50nm in size at different conditions. Owing to the unique structure, the obtained MoO2/CF composite exhibits a high reversible specific capacity of 690mAhg−1 after 200 cycles at 500mAg−1, and even displays 576mAhg−1 at 1000mAg−1 after 200 cycles. The improved electrochemical performance suggests that MoO2/CF composite is a promising anode material for lithium ion storage.