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The waste disposal crisis in Southern Italy has led to a phenomenon dubbed 'the Land of Fires,' where illegal waste disposal and toxic fires of waste are currently contaminating the land, the ground and surface water, and the air quality. The general aim of this study was to investigate the psychosocial factors involved in the prediction of municipal solid waste separation, in a convenient sample of the inhabitants of three areas of Southern Italy, that is specifically the Land of Fires territory (Campania region), Abruzzo and Puglia. We put forward a model involving both pro-environmental concerns and cognitive evaluations. A written questionnaire was administered to a sample of 313 inhabitants from the three areas. Structural equation modelling was performed on the data. The findings confirmed the hypothesized relationships between study variables. The results showed that internal attribution and social norms were the strongest predictors of attitude, followed by the level of knowledge. Biospheric and altruistic values weakly predicted attitudes. Attitude strongly predicted the behavioural intention, which in turn predicted pro-environmental behaviour (i.e. recycling). Trust in institutions was unrelated to the recycling attitude. Attitudes partially mediated the relationship between internal attribution and behavioural intention, and between social norms and behavioural intention. Based on those results, some suggestions are put forward to improve recycling behaviour in the relevant territories. [ABSTRACT FROM AUTHOR]