Ecological momentary assessment (EMA) may elicit physical activity (PA) estimates that are less prone to bias than traditional self-report measures while providing context. The objective of this study was to examine the convergent validity of EMA-assessed PA compared with accelerometry. The participants self-reported their PA using International Physical Activity Questionnaire (IPAQ) and Behavioral Risk Factor Surveillance System (BRFSS) and wore an accelerometer while completing daily EMAs (delivered through the mobile phone) for 7 days. Weekly summary estimates included sedentary time and moderate-, vigorous-, and moderate-to vigorous-intensity physical activity (MVPA). Spearman coefficients and Lin's concordance correlation coefficients (LCC) examined the linear association and agreement for EMA and the questionnaires as compared with accelerometry. Participants were aged 43.3 (SD 13.1) years, 51.7% (123/238) were African American, 74.8% (178/238) were overweight or obese, and 63.0% (150/238) were low income. The linear associations of EMA and traditional self-reports with accelerometer estimates were statistically significant (P<.05) for sedentary time (EMA: ρ=.16), moderate-intensity PA (EMA: ρ=.29; BRFSS: ρ=.17; IPAQ: ρ=.24), and MVPA (EMA: ρ=.31; BRFSS: ρ=.17; IPAQ: ρ=.20). Only EMA estimates of PA were statistically significant compared with accelerometer for agreement. The mobile EMA showed better correlation and agreement to accelerometer estimates than traditional self-report methods. These findings suggest that mobile EMA may be a practical alternative to accelerometers to assess PA in free-living settings.