Background: This study aimed to develop and assess the psychometric features of the Physical Activity at Workplace Questionnaire (PAWPQ) based on the Social Cognitive Theory (SCT) to evaluate employees' physical activity (PA) behaviors at the workplace. Methods: This psychometric cross-sectional study was conducted on 455 employees working in one of the gas refineries in Iran. The participants were selected using the proportional stratified sampling method in 2019. The data collection tools were a demographic information questionnaire, the short form of the International Physical Activity Questionnaire (IPAQ), and a questionnaire developed based on the SCT, whose psychometric features were confirmed in terms of validity and reliability. Data were analyzed using SPSS22 and AMOS20 software. Results: The first version of PAWPQ-SCT had 74 items. After evaluating content and face validity, nine items were removed. The results of the content validity index (0.98), content validity ratio (0.86), and impact score (3.62) were acceptable for the whole instrument. In exploratory factor analysis, after removing seven items—58-item final version of the scale—six factors could explain 73.54% of the total variance. The results of structural equation modeling showed the acceptable fit of the model into the data (RMSEA = 0.052, CFI = 0.917, NFI = 0.878, TLI = 0.905, IFI = 0.917, CMIN/DF = 2.818). Cronbach's alpha coefficient and Intraclass Correlation were 0.90 and 0.86, respectively. Conclusion This study confirmed that the psychometric features of the 58-item final version of PAWPQ-SCT constructs were acceptable in a sample of Iranian employees. This questionnaire can be used as a valid and reliable tool to evaluate Iranian employees' PA behaviors and develop effective educational interventions for workers and managers.