The employment landscape has changed significantly over the past few years in emerging economies including Ghana where many people are rapidly transitioning from livelihood activities that originally involved physical exertion to work environments where performance of duties are mostly non-physical. Working under non-active conditions could, however, exacerbate the risk of developing chronic diseases that are increasingly becoming problematic in many developing countries. Drawing on a cross-sectional nationally representative sample data of 4425 adult Ghanaian workers collected by the WHO Study on Global Ageing and Adult Health in developing countries, we examined the relationship between occupational physical activity and hypertensive status. We employed the complementary log–log analysis technique to build nested models with results presented in odds ratios. After controlling for several relevant variables, the results show that performing sedentary related work (AOR = 1.23, CI = 1.06–1.42) is significantly associated with a higher likelihood of being hypertensive compared with those whose work involved moderate physical activity. Other factors that were significantly associated with being hypertensive included tobacco use (AOR = 1.33, CI = 1.05–1.70), living in an urban environment (AOR = 1.15, CI = 1.01–1.32), and being a female (AOR = 1.18, CI = 1.01–1.37) and being an older person. Policies on reducing the risk of developing chronic conditions especially hypertension need to recognize the contributions of the work environment in emerging developing economies.