Similar to cupric oxides and sulfides, the nitrogen-containing analogue copper carbodiimide (CuNCN) is considered as a potentially promising photoelectric material. However, there is lack of fundamental investigations on controllable synthesis and photoelectric properties of CuNCN nano/microcrystals. Herein, a facile method was developed to synthesize high-quality CuNCN semiconductor microcrystals with different sizes and hierarchical nanostructures at room temperature. This reaction was carried out in aqueous solutions, avoiding the involvement of non-aqueous solutions and high temperature solid phase reaction during the synthesis of CuNCN microcrystals. Photoelectric response of as-prepared CuNCN microcrystals was first observed under the irradiation of visible light at room temperature. The aqueous synthetic route can also provide an inspiration to acquire other metal carbodiimides nano/microcrystals. (C) 2015 Elsevier B.V. All rights reserved.