Expertise with print is likely to optimize visual processes for recognizing characters of a familiar writing system. Although brain activations have been identified for words and letter strings in contrast with other stimuli, relatively little work has focused on the neural basis of single-letter perception. English readers and Chinese-English bilinguals participated in an ERP study and performed a 1-back identity judgment on Roman letters, Chinese characters, pseudofonts, and their string versions. The Chinese-English bilinguals showed an enhanced N170 for both Roman letters and Chinese characters relative to pseudofonts. For the non-Chinese readers, the N170 amplitude was larger for Roman letters relative to Chinese characters and pseudofonts. Our results suggest that changes in relatively early visual processes underlie expert letter perception.