Writing stands as one of humanity’s most profound inventions, facilitating the efficient sharing and transmission of vast amounts of information. Similar to images and facial expressions, visual (written) words possess the ability to evoke emotional connotations. Understanding how the brain perceives these emotional nuances encoded in highly symbolic visual words is a key focus of the emerging field of “affective neurolinguistics.” At the core of this inquiry lies the examination of the early posterior negativity (EPN), an event-related potentials (ERPs) component peaking around 300 ms after stimulus onset in the occipitotemporal scalp region. EPN has consistently emerged in response to emotional stimuli, encompassing pictures, faces, and visual words. However, prior research has notably lacked observation of EPN in response to Chinese emotional words, raising questions about potential differences in emotional processing between Chinese and other languages. Given the logographic nature of the Chinese writing system and the prevalence of compound words in the Chinese lexicon, this study aims to explore whether the emotional processing of Chinese monomorphic and compound words elicits an EPN response. Two experiments were conducted: Experiment 1 utilized one-character words (monomorphic words), while Experiment 2 employed two-character words (compound words). Participants were assigned a go/no-go task, instructed to respond to unknown words (word recognition task) or blue stimuli (color decision task). Data analysis using a data-driven mass univariate approach revealed significant ERP differences between emotional and neutral words. Notably, the time course, scalp topography, and cortical generators of the difference ERP presented a characteristic EPN response in both experiments. These findings strongly support the notion that the processing of emotional connotations in both Chinese monomorphic and compound words is reflected by the EPN, paving the way for future research using EPN as an emotion-related ERP component for investigating emotional processing of Chinese words.