Phenylboronic acid (PBA) is recognized as one of the most promising cancer cell binding modules attributed to its potential to form reversible and dynamic boronic ester covalent bonds. Exploring the advanced chemical versatility of PBA is crucial for developing new anticancer therapeutics. The presence of a specific Lewis acidic boron atom-based functional group and a Π-ring-connected ring has garnered increasing interest in the field of cancer immunotherapy. PBA-derivatized functional biomaterials can form reversible bonds with diols containing cell surface markers and proteins. This review primarily focuses on the following topics: (1) the importance and versatility of PBA, (2) different PBA derivatives with pKa values, (3) specific key features of PBA-mediated biomaterials, and (4) cell surface activity for cancer immunotherapy applications. Specific key features of PBA-mediated materials, including sensing, bioadhesion, and gelation, along with important synthesis strategies, are highlighted. The utilization of PBA-mediated biomaterials for cancer immunotherapy, especially the role of PBA-based nanoparticles and PBA-mediated cell-based therapeutics, is also discussed. Finally, a perspective on future research based on PBA-biomaterials for immunotherapy applications is presented.