In this paper, hex-pod-like Cu2O whiskers were successfully synthesized from a Cu(CH3COO)(2) precursor under hydrothermal conditions, and examined by means of scanning electron microscopy, X-ray microprobe analysis, and X-ray diffraction. The effects of precursor concentration and pH, reaction temperature and time on the evolution of Cu2O synthesis and morphology were investigated. The whiskers were cornposed of a nucleus and six pods. The pods grow along the [0 0 1] directions, and are bounded to {0 01} faces. The adjacent pods are perpendicular to each other. The dipolar characteristics of the Cu2O {0 01} faces are the critical factors in the synthesis of the peculiar Cu2O whiskers. Finally, a possible growth mechanism is proposed. (C) 2002 Elsevier Science B.V. All rights reserved.