In this paper we show by means of 'in situ' x-ray diffraction studies that CuTCNQ formation from Cu(solid)-TCNQ(solid tetracyanoquinodimethane) goes through Cu diffusion at room temperature. The film quality depends on the TCNQ evaporation rate. At low evaporation rate we get a single phase-I CuTCNQ film very well crystallized and well oriented. The film has a CuTCNQ(0 2 0) orientation. The film is formed by CuTCNQ nanorods of a very homogeneous size. The film homogeneity has also been seen by atomic force microscopy (AFM). The electronic properties of the film have been measured by x-ray photoelectron spectroscopy (XPS) and ultra-violet photoelectron spectroscopy (UPS). Thus, the Cu-diffusion method has arisen as a very simple, clean and efficient method to grow localized CuTCNQ nanorods on Cu, opening up new insights for technological applications.