Readers of Chinese characters need to recognise how they are formed in order to identify them correctly. However, our understanding of the cognitive processing of characters in working memory is limited. Using the character N-back task paradigm, electrophysiological data were recorded from 30 participants to investigate the effects of the number of radicals and from 30 participants to investigate the effects of the function of radicals on neural activity during the recognition, updating, and maintenance of characters in working memory. Results showed that compound and irregular characters were less correct and required longer response times than single-component and regular characters. In addition, the compound character condition had more negative N2pc, lower P300 and lower SW amplitude than the single-component character condition. Meanwhile, there was a larger P200 in the irregular character condition than in the regular character condition, but there was no difference between the regular character and the irregular character in the N2pc, P300, and SW components. The number of radicals and the function of the radicals may have different effects on the character processing. This study reveals the neural effects of Chinese character radicals on cognitive processing in a working memory task and provides behavioral and electrophysiological evidence for a theoretical model of verbal working memory subprocesses.