Electrochemical behavior of atorvastatin (AT) and optimum conditions to its quantitative determination were investigated using voltammetric methods. Some electrochemical parameters such as diffusion coefficient, surface coverage of adsorbed molecules, electron transfer coefficient, standard rate constant and number of electrons were calculated using the results of cyclic voltammetry. A tentative mechanism for the oxidation for AT has been suggested. The oxidation signal of AT molecule was used to develop fully validated, new, rapid, selective and simple square-wave anodic adsorptive stripping voltammetric (AdsSWV) and differential pulse anodic stripping voltammetric (AdsDPV) methods to direct determination of AT in pharmaceutical dosage forms and biological samples. For the AdsDPV and AdsSWV techniques, linear working ranges were found to be 1.0 × 10 -7 -5.0 × 10 -6 and 3.0 × 10 -7 -5.0 × 10 -6 mol l -1 , respectively. The detection limits obtained from AdsDPV and AdsSWV were calculated to be 6.55 × 10 -8 and 1.53 × 10 -7 mol l -1 , respectively. The methods were successfully applied to assay the drug in tablets, human blood serum and human urine.