The effects of high-temperature supercritical CO2 (SC-CO2) extraction on Z-isomerization and recovery of carotenoids (astaxanthin, adonirubin, and adonixanthin) from Paracoccus carotinifaciens are investigated. The high-temperature extraction, especially at >100 degrees C, not only increases the total Z-isomer ratio of carotenoids in the resulting extracts but also improves carotenoid recovery. For example, when the SC-CO2 extraction is performed at 60 degrees C and 30 MPa with an entrainer (ethanol), the total Z-isomer ratio and the recovery of astaxanthin are 11.1% and 28.4%, respectively, whereas at 120 degrees C, the values increase to 54.2 and 56.4%, respectively. The significant improvement in the extraction efficiency of carotenoids at high temperatures can be attributed to the increase in the ratio of carotenoid Z-isomers with high solubility in SC-CO2. Moreover, the effects of extraction pressure and entrainer content on Z-isomerization and recovery of carotenoids are also investigated. The results show that higher pressure and ethanol content resulted in lower Z-isomer ratios and higher recoveries of carotenoids. As the Z-isomers of carotenoids have greater bioavailability and potentially exhibit superior biological activities than the all-E-isomers, high value-added carotenoids, and higher yield can be simultaneously achieved with high-temperature extraction. Practical applications: As carotenoid extraction is usually performed using toxic organic solvents, residual solvents are a serious concern. In addition, naturally occurring carotenoids (mainly the all-E-isomers) have low bioavailability. These are important issues that need to be overcome for the industrial use of carotenoids. The Z-isomer-rich carotenoids obtained by SC-CO2 extraction under high-temperature conditions have great potential to solve these issues simultaneously.