This paper presents research results on new syllable structures for the Portuguese language. The location of the syllable boundaries is a well known problem of nonconsensual resolution in Portuguese, mainly when the acoustic-phonetic constraints are taken into account. Based on various acoustic-phonetic restrictions of Portuguese speech, new syllable splitting rules were studied in a corpus of 400K Portuguese words. All these words were automatically converted into sequences of C (consonants) and V (vowels) and also related to the new syllable structures. When syllable structures were outlined in a statistical form, some mapping confirmed our expectations, others apparently ran against the expectations and others appeared to be new. These results provide clues about Portuguese syllabification architecture and can also guide the development of improved complementary models for syllable processing in speech applications.