The PPP–RTK method, which combines the concepts of Precise of Point Positioning (PPP) and Real-Time Kinematic (RTK), is proposed to provide a centimeter-accuracy positioning service for an unlimited number of users. Recently, the PPP–RTK technique is becoming a promising tool for emerging applications such as autonomous vehicles and unmanned logistics as it has several advantages including high precision, full flexibility, and good privacy. This paper gives a detailed review of PPP–RTK focusing on its implementation methods, recent achievements as well as challenges and opportunities. Firstly, the fundamental approach to implement PPP–RTK is described and an overview of the research on key techniques, such as Uncalibrated Phase Delay (UPD) estimation, precise atmospheric correction retrieval and modeling, and fast PPP ambiguity resolution, is given. Then, the recent efforts and progress are addressed, such as improving the performance of PPP–RTK by combining multi-GNSS and multi-frequency observations, single-frequency PPP–RTK for low-cost devices, and PPP–RTK for vehicle navigation. Also, the system construction and applications based on the PPP–RTK method are summarized. Moreover, the main issues that impact PPP–RTK performance are highlighted, including signal occlusion in complex urban areas and atmosphere modeling in extreme weather events. The new opportunities brought by the rapid development of low-cost markets, multiple sensors, and new-generation Low Earth Orbit (LEO) navigation constellation are also discussed. Finally, the paper concludes with some comments and the prospects for future research.