An observational study of young Italian NEETs (not in education, employment or training) and their EET peers (in education, employment or training) was conducted in the framework of a European Union (EU) project. Main characteristics and behaviours were compared to gain insights into the NEET condition in Italy. The sample included 111 NEETs (males = 73) and 117 EETs (males = 106) aged 16 to 23 years, belonging to comparable socio-demographic backgrounds. A self-report questionnaire was prepared to gain general information and investigate psychological well-being and behaviours. Most of the sample reported good relationships with parents. Education level and addictive behaviours were significantly different between NEETs and EETs while psychological well-being was not significantly different in relation to thoughts of suicide, unpleasant thoughts, weakness in the morning and nervousness. The heterogeneity of NEETs and the role of socio-cultural background in their psychophysical discomfort were highlighted. However, differently from reported in the literature, NEET adolescents sampled in this study, particularly those without social or family problems, did not show higher percentages of health or psychological problems when compared to their peer EETs. Furthermore, NEETs did not focus on the problem of their status, which also reflects a vague idea of the future.