A number of behavioral studies have suggested that syllables might play an important role in visual word recognition in some languages. We report two event-related potential (ERP) experiments using a new paradigm showing that syllabic units modulate early ERP components. In Experiment 1, words and pseudowords were presented visually and colored so that there was a match or a mismatch between the syllable boundaries and the color boundaries. The results showed color-syllable congruency effects in the time window of the P200. Lexicality modulated the N400 amplitude, but no effects of this variable were obtained at the P200 window. In Experiment 2, high- and low-frequency words and pseudowords were presented in the congruent and incongruent conditions. The results again showed congruency effects at the P200 for low-frequency words and pseudowords, but not for high-frequency words. Lexicality and lexical frequency effects showed up at the N400 component. The results suggest a dissociation between syllabic and lexical effects with important consequences for models of visual word recognition.