In Cu(Ⅱ)-C_2O_4~(2-)-NH_3-NH_4~+-H_2O system, complicated copper oxalate powders were synthesized by coordination- precipitation process with ammonium oxalate as precipitating agent. The composition and morphology of the powders were characterized by chemical analysis, X-ray diffraction (XRD), scanning electron microscopy (SEM), infrared spectroscopy (IR), and thermogravimetric and differential thermal analysis (TGA-DTA). The effects of temperature, copper ion concentration and pH value were investigated. The experimental results show that pure copper oxalate hydrate is prepared below a critical pH value of 6.0, whereas the powder turns to be a complicated copper salt combined with NH_3 over the pH value. Probable chemical formula, CuC_2O_4·x(NH_3) ·yH_2O can be assumed, where x and y relate to experimental conditions. Technological parameters, such as temperature, initial copper concentration and solution pH value, have significant effects on particle size, morphology and dispersion of the powders. Powders with various morphologies, pie shape, spindle shape and rod shape, can be synthesized under certain technological conditions.