Previous authors have shown that orthographic experience modifies phonological awareness, yet whether it also impacts on automatic speech processing has not been explored. In the present study, we replicated the effect of early orthographic experience on phonological awareness, and further demonstrated that on-line speech processing varied between readers coming from different literacy backgrounds. We measured phonological awareness and on-line speech processing by a sound matching and a primed shadowing task, respectively. Participants were Cantonese-Chinese speakers who had learned only logographic characters for their Chinese reading, and those who had learned both characters and alphabetic Pinyin. We found evidence of phoneme-level analysis in both sound matching and primed shadowing only in the latter group. This finding suggests an active role of orthographic experience in shaping phonological awareness and the representation subserving day-to-day speech communication.