This study was conducted to investigate how syllables and lexical tones are processed in Cantonese speech production using the picture-word interference task with concurrent recording of event-related brain potentials (ERPs). Cantonese-speaking participants were asked to name aloud individually presented pictures and ignore an accompanying auditory word distractor. The target and distractor either shared the same word-initial syllable with the same tone (Tonal-Syllable related), the same word-initial syllable without the same tone (Atonal-Syllable related), the same tone only (Tone alone related), or were phonologically unrelated. Participants’ naming responses were faster, relative to an unrelated control, when the target and distractor shared the same tonal- or atonal-syllable but null effect was found in the Tone alone related condition. The mean ERP amplitudes (per each 100-ms time window) were subjected to stimulus-locked (i.e., time-locked to stimulus onset) and response-locked (i.e., time-locked to response onset) analyses. Significant differences between related and unrelated ERP waves were similarly observed in both Tonal-Syllable related and Atonal-Syllable related conditions in the time window of 400–500 ms post-stimulus. However, distinct ERP effects were observed in these two phonological conditions within the 500-ms pre-response period. In addition, null effects were found in the Tone alone related condition in both stimulus-locked and response-locked analyses. These results suggest that in Cantonese spoken word production, the atonal syllable of the target is retrieved first and then associated with the target lexical tone, consistent with the view that tone has an important role to play at a late stage of phonological encoding in tonal language production.