This work reports the development of a dimethylglyoxime (DMG) modified sensor in which the complexing agent was successfully immobilized by drop-casting onto a screen-printed carbon electrode support (SPCE). The experimental conditions for the preparation of the DMG-SPCE sensor were optimized by means of a D-optimal design, and the built sensors were analytically evaluated for the determination of Ni(II) by adsorptive stripping voltammetry (AdSV). Its analytical performance suggests its suitability for the determination of Ni(H)-ions by AdSV at concentration levels of mu g L-1 (LOD of 2.3 mu g L-1, linear range from 7.6 to 200 mu g L-1). Finally, the applicability of the developed sensor was assessed by the determination of trace levels of Ni(II) by AdSV in a wastewater reference material with a very high reproducibility (0.005%) and good trueness (0.1%).