In Serbian, lexical decision latencies to words composed of letters that exist in both the Roman and Cyrillic alphabets (some of which have different phonemic interpretations in each) are slower than for the unique alphabet transcription of those same words. In this study, we use the effect of phonological ambiguity to explore the time course of semantic facilitation. Targets are either the phonologically ambiguous forms (e.g., PETAK meaning “Friday” when pronounced as a Roman string /petak/ but without meaning when pronounced in Cyrillic as /retak/) or the unique alphabet transcription of the same word (ПETAK). We manipulate alphabet match and semantic relatedness of prime to target. In addition to replicating slowing due to phonological ambiguity, we show 1) greater alphabet switch cost for bivalent then for unambiguous targets as well as for unrelated then for related prime-target pairs and 2) greater semantic facilitation as the number of shared common letters between prime and target increases. Results reveal the interaction of phonological and semantic processes in Serbian. The findings are discussed in terms of a triangle model of language processing, which hypothesizes a division of labor between an orthography-to-semantics, and an orthographyto-phonology-to-semantics route and their simultaneous contribution to activation of meaning.