Among the neuroleptics, atypical antipsychotics have received great attention in recent years, because of their peculiar pharmacological profile. Due to their widespread use, rapid, efficient and economical methods of analysis of these compounds in pharmaceutical formulations and biological fluids are required, and in this sense electrochemical techniques appear particularly a:tractive. Most of these compounds are reported to be electroactive but quantification at classic electrodes is often unsuitable due to electrode fouling and absence or reduced linearity between concentration and current intensity. A gold electrode modified with oxidized single walled carbon nanotubes has preyed useful to overcome these problems. A deep insight into the electrochemistry of these compounds is reported, with the aid of Mass Spectrometry and DFT (Density Functional Theory) calculation; in particular, a computational approach to the electrochemistry of these substances turned out to be really useful to the purpose. A voltammetric method for the determination of risperidone and olanzapine, two widely used atypical antipsychotics, has also been setup. (C) 2012 Elsevier B.V. All rights reserved.