Morphologically complex words are common across different languages, especially in Chinese, because more than 90% of common modern Chinese words are complex words. Many behavioral studies have suggested the whole-word processing of Chinese complex words, but the neural correlates of whole-word processing remain unclear. Previous electrophysiological studies revealed automatic and early (∼250 ms) access to the orthographic forms of monomorphic words in the ventral occipitotemporal area. In this study, we investigated whether there is also automatic and early orthographic recognition of Chinese complex words (as whole units) by recording event-related potentials (ERPs). A total of 150 two-character words and 150 two-character pseudowords composed of the same 300 characters (morphemes) were pseudorandomly presented to proficient Chinese readers. Participants were required to determine the color of each stimulus in the color decision task and to determine whether each stimulus was a word in the lexical decision task. The two constituent characters of each stimulus were horizontally arranged in Experiment 1 and vertically arranged in Experiment 2. The results revealed a significant early ERP difference between words and pseudowords approximately 250–300 ms after stimulus onset in the parieto-occipital scalp region. The early ERP difference was more prominent in the color decision task than in the lexical decision task, more prominent in Experiment 1 than in Experiment 2, and more prominent in the left parieto-occipital scalp region than in the right. Source analysis results showed that the early ERP difference originated from the left ventral occipitotemporal cortex. These results reflected early and automatic access to whole-word orthographic representations of Chinese complex words in the left ventral occipitotemporal cortex.