One of the several differences between Modern European Portuguese (EP) and Modern Brazilian Portuguese (BP) is the prepositional expression of complements licensed by the preposition a. While in EP the preposition a occurs in several contexts, this element has been substituted by other strategies in BP, as is extensively discussed in the literature. The aim of this paper is to investigate the historical behavior of a-marked prepositional accusatives (PP-ACC) in Portuguese. In order to do so, a search was conducted for PP-ACCs in the Historical Portuguese Corpus Tycho Brahe. The results showed an increase of PP-ACCs in the 17th century, followed by a decrease in the 18th century. Thereafter, unmarked accusatives (NP-ACC) were analyzed in the corpus, which resulted in 7756 sentences, contrasting with 624 PP-ACCs in the same contexts. This result shows that the a-marked accusative is far less common than bare accusatives in Historical Portuguese. Psych verbs, however, behaved differently, showing a constant increase in PP-ACCs. In EP, the preposition a still introduces Experiencer arguments in structures with some psych verbs (O vinho agradou ao João—lit. ‘The wine pleased ‘to’ John’). In BP, the preposition a has disappeared in psych predicates (O vinho agradou Ø o João—‘The wine pleased John’). In both Modern EP and BP, most PP-ACCs have become typical unmarked direct objects. In the context of psych verbs, however, structural accusative assignment has shifted to structural dative Case in Modern EP, so as to ascertain the interpretation of the Experiencer in the internal argument via the preposition a. While in Modern BP, the argument is not overtly marked since it receives inherent accusative case in the derivation.