The adverse effects of ambient particulate matter (PM) on human health have been well demonstrated, but the underlying properties responsible for its toxicity are still unclear. We hypothesized that particulate radioactivity, which is due to the attachment of radioactive nuclides on particle surfaces, may be responsible for part of PM toxicity. We measured the gross α- and β-activities for daily PM2.5 and PM10 filters collected at the Harvard Supersite in downtown Boston from 2005 to 2006 and calculated the radioactivities at the time of air sampling retrospectively based on a previously established formula. We examined the relationship between different radioactivities and compared our measurements to those measured at the Boston EPA RadNet Station. The results showed that the majority of PM10 radioactivity is associated with that of PM2.5 samples for both α-activity (98%) and β-activity (83%). A strong linear relationship was observed between the α- and β-activities for both PM2.5 [slope = 0.47 (±0.03); p-value < 0.0001] and PM10 [slope = 0.46 (±0.09); p-value < 0.0001] samples. Measurements at the Harvard Supersite and at EPA RadNet sites are highly correlated for both α-activities [slope = 0.17 (±0.02), p-value < 0.0001] and β-activities [slope = 0.30 (±0.05), p-value < 0.0001]. Additionally, we identified several significant predictors for PM2.5 α-activities. This novel method we developed to measure α- and β-activities from archived filters will make it possible to assess the retrospective particle radioactivity exposure for future epidemiological studies.