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Air pollution has far-reaching environmental and social consequences, requiring the active participation of individual citizens in improving air quality by means of emission-reducing behaviors. This research examines the relationship between citizens’ knowledge, perceptions of air quality, attitudes towards policy measures, and intentions to adopt environmentally-friendly behaviors to combat air pollution. A comprehensive survey is conducted among a representative sample from seven regions in the Po basin area: Emilia-Romagna, Friuli-Venezia Giulia, Lombardy, Piedmont, Province of Trento, Valle d’Aosta, and Veneto. The survey aims at profiling participants based on their level of information, perceptions of air pollution, and attitudes towards emission-reducing behaviors. Cluster analysis identifies meaningful differences among citizen groups in terms of their awareness and intentions to engage in specific behaviors. Four distinct clusters emerge, each characterized by varying levels of willingness to embrace pro-environmental behaviors and support air quality improvement initiatives. By examining these profiles, the study uncovers patterns in citizens’ awareness, concerns, and acceptance of environmentally-friendly practices. The findings offer valuable insights for policymakers to develop targeted interventions, policies, and communication strategies.