Exposure to high levels of fine particulate matter (PM) with aerodynamic diameter () via air pollution may be a risk factor for psychiatric disorders during adulthood. Yet few studies have examined associations between exposure and the trajectory of symptoms across late childhood and early adolescence. The current study evaluated whether exposure at 9-11 y of age affects both concurrent symptoms as well as the longitudinal trajectory of internalizing and externalizing behaviors across the following 3 y. This issue was examined using multiple measures of exposure and separate measures of symptoms of internalizing disorders (e.g., depression, anxiety) and externalizing disorders (e.g., conduct disorder), respectively. In a sample of more than 10,000 youth from the Adolescent Brain Cognitive Development (ABCD) Study, we used a dataset of historical levels and growth curve modeling to evaluate associations of exposure with internalizing and externalizing symptom trajectories, as assessed by the Child Behavioral Check List. Three distinct measures of exposure were investigated: annual average concentration during 2016, number of days in 2016 above the US Environmental Protection Agency (US EPA) 24-h standards, and maximum 24-h concentration during 2016. At baseline, higher number of days with levels above US EPA standards was associated with higher parent-reported internalizing symptoms in the same year. This association remained significant up to a year following exposure and after controlling for annual average, maximum 24-h level, and informant psychopathology. There was also evidence of an association between annual average and externalizing symptom levels at baseline in females only. Results suggested exposure during childhood is associated with higher symptoms of internalizing and externalizing disorders at the time of exposure and 1 y later. In addition, effects of exposure on youth internalizing symptoms may be most impacted by the number of days of exposure above US EPA standards in comparison with annual average and maximum daily exposure. https://doi.org/10.1289/EHP13427.