Electrochemical techniques have been successfully employed for the determination of two atypical antipsychotics, aripiprazole and octoclothepin, in pharmaceutical formulations and in biological fluids, with the aim to propose a method alternative to chromatography. We explored as well their electrochemical behavior and the use of DFT (Density Functional Theory) calculations substantially contributed to the rationalization of their electrochemistry. Thus, the mentioned compounds were analyzed in pharmaceutical forms by Linear Scan Voltammetry (LSV). A stripping voltammetric method (AdSV) was optimized for their determination in the mu g L-1 range, concentration expected in biological samples such as urine. (C) 2013 Elsevier B.V. All rights reserved.