Languages may differ in terms of the functional units of word-form encoding used in spoken word production. It is widely accepted that segments are the primary units used in Indo-European languages. However, it is controversial what the functional units (syllables or segments) in Chinese spoken word production are. In the present study, Mandarin Chinese speakers named pictures while ignoring distractor words presented simultaneously, which shared atonal syllables, bodies or rhymes, or were unrelated with the name of the target pictures. Behavioral results showed that naming latencies in the 3 phonologically-related conditions were significantly shorter than those associated with the unrelated condition. EEG data indicated that the syllable-related condition modulated event-related potentials (ERPs) in a time window of 320-500 ms, the body-related condition modulated ERPs from 370-420 ms, while the rhyme-related condition modulated ERPs from 400-450 ms. The starting points for evident syllable, body, and rhyme priming effects were 322 ms, 368 ms, and 408 ms (by the Guthrie & Buchwald method) or 340 ms, 372 ms and 403 ms (by the jackknife procedure), respectively. Our findings provide a relative temporal course of syllable and segment encoding in Chinese spoken naming: Syllables are retrieved before segments, and constitute the primary processing units during the early stage of word-form encoding. Furthermore, segments and their order are retrieved incrementally from left to right when producing Chinese spoken words.