Differential pulse anodic stripping voltammetry was used for trace determination of picoxystrobin in urine and water samples. Experimental conditions have been optimized and the measurement cycle started with the application of a deposition potential at -700 mV, during 60s, for the in situ formation of the Bi film on a glassy carbon substrate and the accumulation of the analyte. It has been proven that, in the conditions employed, a significant amount of Bi is still present as a film on the surface electrode when the anodic scan is performed from +790 to +1050 mV at a rate of 40 mV s(-1) and that the presence of Bi is fundamental for the accumulation and oxidation of picoxystrobin during re-dissolution (peak maximum at +954 mV). The supporting electrolyte was HCl 1 mol L-1 and a cleaning procedure was developed in order to minimize memory effects. Linear and homoscedastic analytical responses (r(2) > 0.99) have been observed with limit of quantification of 100 mu g kg(-1). Solid phase extraction (on a C-18 cartridge) allows the pre-concentration of the analyte and eliminates interferences from urine samples. Recoveries from 89.3 to 104.8% were found and interferences from azoxystrobin, dimoxistrobin, fluxastrobin, kresoximethyl and pyraclostrobin were evaluated. (C) 2013 Elsevier Ltd. All rights reserved.