Recently, a new Multi-Angle Implementation of Atmospheric Correction (MAIAC) algorithm was developed for the MODerate Resolution Imaging Spectroradiometer (MODIS) which provides Aerosol Optical Depth (AOD) at 1 km resolution. The relationship between MAIAC AOD and PM<sub>2.5</sub> as measured by 84 EPA ground monitoring stations in the entire New England and the Harvard supersite during 2002–2008 was investigated and also compared to the AOD/PM<sub>2.5</sub> relationship using conventional MODIS 10 km AOD retrieval (MYD04) for the same days and locations. The correlations for MYD04 and for MAIAC are <i>r</i> = 0.62 and 0.65, respectively, suggesting that AOD is a reasonable proxy for PM<sub>2.5</sub> ground concentrations. The slightly higher correlation coefficient (<i>r</i>) for MAIAC can be related to its finer resolution resulting in better correspondence between AOD and EPA monitoring sites. Regardless of resolution, AOD/PM<sub>2.5</sub> relationship varies daily, and under certain conditions it can be negative (due to several factors such as an EPA site location (proximity to road) and the lack of information about the aerosol vertical profile). By investigating MAIAC AOD data we found a substantial increase, by 50–70% in the number of collocated AOD vs PM<sub>2.5</sub> pairs, as compared to MYD04, suggesting that MAIAC AOD data is more capable in capturing spatial patterns of PM<sub>2.5</sub>. Importantly, the performance of MAIAC AOD retrievals remains reliable under partly cloudy conditions when MYD04 data are not available, and it can be used to significantly increase the number of days for PM<sub>2.5</sub> spatial pattern prediction based on satellite observations.