Abstract Data from a three-dimensional lightning mapping array (LMA) and from two soundings by balloon-borne electric field meters (EFMs) were used to analyze the electrical structures of a multicell storm observed on 25 June 2000 during the Severe Thunderstorm Electrification and Precipitation Study (STEPS). This storm had a complex, multicell structure with four sections, each of whose electrical structure differed from that of the others during all or part of the analyzed period. The number of vertically stacked charge regions in any given section of the storm ranged from two to six. The most complex charge and lightning structures occurred in regions with the highest reflectivity values and the deepest reflectivity cores. Intracloud flashes tended to concentrate in areas with large radar reflectivity values, though some propagated across more than one core of high reflectivity or into the low-reflectivity anvil. Intracloud lightning flash rates decreased as the vertical extent and maximum value of reflectivity cores decreased. Cloud-to-ground flash rates increased as cores of high reflectivity descended to low altitudes. Most cloud-to-ground flashes were positive. All observed positive ground flashes initiated between the lowest-altitude negative charge region and a positive charge region just above it. The storm’s complexity makes it hard to classify the vertical polarity of its overall charge structure, but most of the storm had a different vertical polarity than what is typically observed outside the Great Plains. The electrical structure can vary considerably from storm to storm, or even within the same storm, as in the present case.