Background: Limited data are available regarding the correlation between questionnaire and device-measured physical activity (PA) and sedentary behavior (SB) in older women. Methods: We evaluated these correlations in 5,992 women, aged 63 and older, who completed the Women’s Health Initiative (WHI) and Community Healthy Activities Model Program for Seniors (CHAMPS) PA questionnaires and the CARDIA SB questionnaire prior to wearing a hip-worn accelerometer for 7 consecutive days. Accelerometer-measured total, light, and moderate-to-vigorous PA (MVPA), and total SB time were defined according to cutpoints established in a calibration study. Spearman coefficients were used to evaluate correlations between questionnaire and device measures. Results: Mean time spent in PA and SB was lower for questionnaire than accelerometer measures, with variation in means according to age, race/ethnicity, body mass index, and functional status. Overall, correlations between questionnaires and accelerometer measures were moderate for total PA, MVPA, and SB (r ≈ 0.20–0.40). Light intensity PA correlated weakly for WHI (r ≈ 0.01–0.06) and was variable for CHAMPS (r ≈ 0.07–0.22). Conclusion: Questionnaire and accelerometer estimates of total PA, MVPA, and SB have at best moderate correlations in older women and should not be assumed to be measuring the same behaviors or quantity of behavior. Light intensity PA is poorly measured by questionnaire. Because light intensity activities account for the largest proportion of daily activity time in older adults, and likely contribute to its health benefits, further research should investigate how to improve measurement of light intensity PA by questionnaires.