The nucleation mechanisms of copper during electrodeposition of thin films from sulfate solutions were studied by utilizing the electrochemical techniques (cyclic voltammetry and chronoamperometry) and atomic force microscopy (AFM). Near atomically smooth glassy carbon was used as the deposition substrate (electrode). The copper nucleation mechanisms were examined as a function of solution pH, copper concentration, deposition potential, temperature, and background electrolyte. It was found that with pH and copper concentration increase, the nuclei size increased, while the nuclei population density decreased. An increase of deposition potential produced smaller nuclei and higher nuclei population density. Temperature affected the morphology of deposited copper. The presence of background electrolyte also influenced the morphology and population density of copper nuclei. The nucleation mechanisms were examined by fitting the experimental data (chronoamperometry) into the Scharifker-Hills nucleation models. It was found that at pH 1, in the absence of background electrolyte, copper nucleation was instantaneous. At pH 2 and 3, the mechanism was inconclusive. In the presence of background electrolyte, the mechanism at pH 1 and 2 was mixed, while at pH 3, the mechanism was progressive nucleation.