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The reaction pathways of CO oxidation over the (1 0 0), (1 1 0) and (1 1 1) crystal planes of Cu 2 O. • Morphologies of Cu 2 O micro/nanocrystals were controlled by simply changing precursor concentration. • Increase of precursor concentration results in more exposure of active crystal plane of Cu 2 O. • Activity of CO self-sustained catalytic combustion on Cu 2 O increases with precursor concentration. • Coordination unsaturated Cu and O on the (1 1 1) and (1 1 0) planes promote CO oxidation. The self-sustained catalytic combustion is one of the most effective ways to remove high concentration CO at low temperature. In this paper, Cu 2 O micro/nanocrystals with different morphologies were successfully synthesized by changing the precursor concentration using liquid phase reduction method. The obtained Cu 2 O were characterized using SEM, XRD, XPS, H 2 -TPR and O 2 -TPD, and the relationship between the catalytic performance and morphology was analyzed based on CO-TPD-MS and activity evaluation results. It was found that high precursor concentration leads to more exposure of active crystal planes of Cu 2 O. Compared with Cu 2 O-1 exposing only (1 0 0) crystal planes, Cu 2 O-5, the precursor concentration of which is 5 times of Cu 2 O-1, exposes (1 0 0) and (1 1 0) crystal planes. Cu 2 O-9, with 9 times of precursor concentration of Cu 2 O-1, exposes (1 0 0), (1 1 0) and (1 1 1) crystal planes simultaneously. All the obtained Cu 2 O with different precursor concentrations can achieve self-sustained CO catalytic combustion, and the catalytic activity increases with increasing precursor concentration (Cu 2 O-1 < Cu 2 O-5 < Cu 2 O-9). The results prove that unsaturated coordination of Cu and O on the (1 1 1) and (1 1 0) planes can enhance the corresponding reducibility, adsorption and activation of gaseous oxygen, consequently promoting the CO oxidation to CO 2 over Cu 2 O-9. [ABSTRACT FROM AUTHOR]