Electrochemical experiments with tetracyanoquinodimethane (TCNQ) modified electrodes in contact with aqueous copper containing electrolytes leads to the incorporation and expulsion of copper ions. This process occurs concomitantly with nucleation and growth processes and significant crystal fragmentation to produce particles with dimensions of the order of 10's of nanometres. During reduction of TCNQ and intercalation of copper ions, different phases of the semiconducting compound CuTCNQ are formed.[1,2] The preparation of both conducting and insulating substrates coated with electroactive TCNQ and CuTCNQ particles of variable size have been made by dip and spin coating procedures. Results suggest that the phase and hence electronic properties of CuTCNQ is dependent on the size of particles that decorate the electrode surface. Combining atomic force microscope (AFM) based methods that interrogate the morphological and electronic properties of nanometre sized particles with use of a scanning electrochemical microscope (SECM) is a new advance in materials characterisation that has proved highly valuable in understanding the highly complex behaviour of these semi-conducting particles.