The particular properties of argumental compounds in Italian pose interesting theoretical challenges, and investigations of possible syntactic operations within this type of complex words have resulted in conflicting conclusions. Regarding compound-internal anaphora, some researchers exclude the possibility that pronouns can refer to the non-head, while others do not. However, these findings have been based on researchers’ intuitions and on occurrences in language corpora, and while intuitions have been shown to give contrasting results, the absence of a grammatical structure in a corpus should not be taken as evidence that the structure is not possible. The present study aims to experimentally determine the possibility of compound-internal pronominal reference based on structural properties of compounds and referential expressions. Judgements were obtained from 140 Italian native speakers who rated the acceptability of sentences containing a pronoun (null or overt) referring to the argument element of an argumental compound. The results indicate that compound-internal anaphoric reference is acceptable in the case of left-headed compounds and, to a somewhat lesser extent, of verb-noun compounds. The argument element of right-headed compounds, however, does not appear to be available to anaphoric reference. Referential expressions also play a role in the degree of acceptability, with left-headed compounds allowing null form anaphora to a greater extent. These results provide new evidence on compound-internal pronominal reference and give important insights into the processing of argumental compounds.