In this work, we investigate the relationships between social network structure and personality; we assess the performances of different subsets of structural network features, and in particular those concerned with ego-networks, in predicting the Big-5 personality traits. In addition to traditional survey-based data, this work focuses on social networks derived from real-life data gathered through smartphones. Besides showing that the latter are superior to the former for the task at hand, our results provide a fine-grained analysis of the contribution the various feature sets are able to provide to personality classification, along with an assessment of the relative merits of the various networks exploited.