Outdoor air pollution has been recognized as a novel environmental neurotoxin. Studies have begun to use brain Magnetic Resonance Imaging (MRI) to investigate how air pollution may adversely impact developing brains. A systematic review was conducted to evaluate and synthesize the reported evidence from MRI studies on how early-life exposure to outdoor air pollution affects neurodevelopment. Using PubMed and Web of Knowledge, we conducted a systematic search, followed by structural review of original articles with individual-level exposure data and that met other inclusion criteria. Six studies were identified, each sampled from 3 cohorts of children in Spain, The Netherlands, and the United States. All studies included a one-time assessment of brain MRI when children were 6–12 years old. Air pollutants from traffic and/or regional sources, including polycyclic aromatic hydrocarbons (PAHs), nitrogen dioxide, elemental carbon, particulate matter (<2.5 or <10 μm), and copper, were estimated prenatally (n = 1), during childhood (n = 3), or both (n = 2), using personal monitoring and urinary biomarkers (n = 1), air sampling at schools (n = 4), or a land-use regression (LUR) modeling based on residences (n = 2). Associations between exposure and brain were noted, including: smaller white matter surface area (n = 1) and microstructure (n = 1); region-specific patterns of cortical thinness (n = 1) and smaller volumes and/or less density within the caudate (n = 3); altered resting-state functional connectivity (n = 2) and brain activity to sensory stimuli (n = 1). Preliminary findings suggest that outdoor air pollutants may impact MRI brain structure and function, but limitations highlight that the design of future air pollution-neuroimaging studies needs to incorporate a developmental neurosciences perspective, considering the exposure timing, age of study population, and the most appropriate neurodevelopmental milestones.