This comprehensive review focuses on polyetheretherketone (PEEK), a synthetic thermoplastic polymer, for applications in dentistry. As a high-performance polymer, PEEK is intrinsically robust yet biocompatible, making it an ideal substitute for titanium—the current gold standard in dentistry. PEEK, however, is also inert due to its low surface energy and brings challenges when employed in dentistry. Inert PEEK often falls short of achieving a few critical requirements of clinical dental materials, such as adhesiveness, osseoconductivity, antibacterial properties, and resistance to tribocorrosion. This study aims to review these properties and explore the various surface modification strategies that enhance the performance of PEEK. Literatures searches were conducted on Google Scholar, Research Gate, and PubMed databases using PEEK, polyetheretherketone, osseointegration of PEEK, PEEK in dentistry, tribology of PEEK, surface modifications, dental applications, bonding strength, surface topography, adhesive in dentistry, and dental implant as keywords. Literature on the topics of surface modification to increase adhesiveness, tribology, and osseointegration of PEEK were included in the review. The unavailability of full texts was considered when excluding literature. Surface modifications via chemical strategies (such as sulfonation, plasma treatment, UV treatment, surface coating, surface polymerization, etc.) and/or physical approaches (such as sandblasting, laser treatment, accelerated neutral atom beam, layer-by-layer assembly, particle leaching, etc.) employed in the literature are summarized and compared. Further, approaches such as the incorporation of bioactive materials, e.g., osteogenic agents, antibacterial agents, etc., to enhance the abovementioned desired properties are explored. This review presents surface modification as a critical and essential approach to enhance the biological performance of PEEK in dentistry by retaining its mechanical robustness.