Five experiments are deseribed which examine how polysyllabic words (e.g., DAY-DREAM, ATHLETE) are stored and retrieved from lexical memory. The first four experiments look at interference effects caused by the accessing of inappropriate lexical entries. It is found that compound nonwords whose first constituent is a word (e.g., DUSTWORTH, FOOTMILGE) take longer to classify as nonwords than compound nonwords whose first constituent is not a word (e.g., TROWBREAK, MOWDFLISK). Moreover, the presence of a word in the second constituent position appears to be irrelevant. These effects hold even when the boundary between constituents is unclear on an orthographic basis (e.g., TRUCERIN). It is also argued that first syllables, as opposed to last syllables, have independent status in the lexicon since nonword first syllables (e.g., ATH) show interference effects, while last syllables (e.g., CULE) do not. The fifth experiment reveals that the frequency of the first constituent of a compound word influences classification times. The results point to the conclusion that polysyllabic words, regardless of whether they are polymorphemic or monomorphemic, are accessed via their first syllable.