Bolus is a kind of auxiliary device used in radiotherapy for the treatment of superficial lesions such as skin cancer. It is commonly used to increase skin dose and overcome the skin-sparing effect. Despite the availability of various commercial boluses, there is currently no bolus that can form full contact with irregular surface of patients’ skin, and incomplete contact would result in air gaps. The resulting air gaps can reduce the surface radiation dose, leading to a discrepancy between the delivered dose and planned dose. To avoid this limitation, the customized bolus processed by three-dimensional (3D) printing holds tremendous potential for making radiotherapy more efficient than ever before. This review mainly summarized the recent development of polymers used for processing bolus, 3D printing technologies suitable for polymers, and customization of 3D printing bolus. An ideal material for customizing bolus should not only have the feature of 3D printability for customization, but also possess radiotherapy adjuvant performance as well as other multiple compound properties, including tissue equivalence, biocompatibility, antibacterial activity, and antiphlogosis.