Activity energy expenditure (AEE) is the modifiable component of total energy expenditure (TEE) derived from all activities, both volitional and nonvolitional. Because AEE may affect health, there is interest in its estimation in free-living people. Physical activity questionnaires (PAQs) could be a feasible approach to AEE estimation in large populations, but it is unclear whether or not any PAQ is valid for this purpose. Our aim was to explore the validity of existing PAQs for estimating usual AEE in adults, using doubly labeled water (DLW) as a criterion measure. We reviewed 20 publications that described PAQ-to-DLW comparisons, summarized study design factors, and appraised criterion validity using mean differences (AEEPAQ − AEEDLW, or TEEPAQ − TEEDLW), 95% limits of agreement, and correlation coefficients (AEEPAQ versus AEEDLW or TEEPAQ versus TEEDLW). Only 2 of 23 PAQs assessed most types of activity over the past year and indicated acceptable criterion validity, with mean differences (TEEPAQ − TEEDLW) of 10% and 2% and correlation coefficients of 0.62 and 0.63, respectively. At the group level, neither overreporting nor underreporting was more prevalent across studies. We speculate that, aside from reporting error, discrepancies between PAQ and DLW estimates may be partly attributable to 1) PAQs not including key activities related to AEE, 2) PAQs and DLW ascertaining different time periods, or 3) inaccurate assignment of metabolic equivalents to self-reported activities. Small sample sizes, use of correlation coefficients, and limited information on individual validity were problematic. Future research should address these issues to clarify the true validity of PAQs for estimating AEE.