The gold electrodeposition process from a glycerol solution on a carbon paste electrode (CPE) was investigated by voltammetry and the morphologies of the electrodeposits were analyzed by scanning electron microscopy (SEM). Voltammetric study indicated that AuCl4− was reduced to Au0 and the process was mixed controlled (mass transport and electron transfer), preceded probably by AuCl4− decomplexation. Glycerol affected the kinetic of gold electrodeposition in function of the AuCl4− concentration. SEM images indicated that the gold electrodeposit covered totally some of the graphite flake by a homogeneous morphology, regardless of the electrodeposition condition. Moreover, using a full factorial planning it was verified that the deposition charge and potential affected the modified CPE performance in a potassium ferrocyanide solution, while HAuCl4 and glycerol concentrations affected only by interactions with the other factors.