We aimed to develop and validate a comprehensive ambient air pollution health literacy instrument. We developed items covering 12 constructs, four information competencies within three health domains. In this population-based telephone interview study, probability proportional to size sampling and random digit dialing were used to determine participants. We conducted confirmatory factor analysis to analyze model fits and used content validity indices and Cronbach’s alpha to measure content validity and internal consistency reliability. Twenty-four items were generated, and a total of 1,297 participants were recruited. A theoretically conceived 12-factor model was supported (root mean square error of approximation [RMSEA] = 0.068, comparative fit index [CFI] = 0.039, standardized root mean square residual [SRMR] = 0.934, normed fit index [NFI] = 0.914, Tucker–Lewis index [TLI] = 0.902). Content validity indices for relevance, importance, and unambiguity were 0.97, 0.99, and 0.94, respectively. Internal consistency reliability assessed by Cronbach’s alpha was 0.93. The ambient air pollution health literacy instrument is valid and reliable and can be used in community residents. The novel instrument can guide the stakeholders and the authority to tailor and implement effective and appropriate interventions and actions, empowering the public to manage hazardous exposure and improving AAPHL of the public.