In recent years, the development of personal protective equipment (PPE) for health care workers (HCWs) attracted enormous attention, especially during the pandemic of COVID-19. The semi-permeable protective clothing and the prolonged working hours make the thermal comfort a critical issue for HCWs. Although there are many commercially available personal cooling products for PPE systems, they are either heavy in weight or have limited durability. Besides, most of the existing solutions cannot relieve the perspiration efficiently within the insolation gowns. To avoid heat strain and ensure a longtime thermal comfort, new strategies that provide efficient personal thermal and moisture management without compromising health protection are required. This paper reviews the emerging materials for protective gown layers and advanced technologies for personal thermal and moisture management of PPE systems. These materials and strategies are examined in detail with respect to their fundamental working principles, thermal and mechanical properties, fabrication methods as well as advantages and limitations in their prospective applications, aiming at stimulating creative thinking and multidisciplinary collaboration to improve the thermal comfort of PPEs.