Polyetheretherketone (PEEK) has become an alternative material for orthopaedics and dental implants. However, bio-inertness is an important limitation in this material. In the present study, a hydroxyapatite (HA)–titanium nitride (TiN) coating was fabricated via pulsed DC magnetron sputtering and treated with hydrothermal treatment to improve the bioactive property of PEEK. The dissolution behavior of the coating was studied in simulated body fluid solution (SBF) at 1, 3, 5, 7, 14, 21, 28, and 56 days. The coating surface was analyzed before and after the immersion process by X-ray photoelectron spectroscopy (XPS), atomic force microscope (AFM), and scanning electron microscope (SEM). The calcium and phosphorus concentration alteration in SBF was quantified by an inductively coupled plasma-optical emission spectrometer (ICP-OES). Coating dissolution and the precipitation of calcium phosphate complex from SBF were observed as occurring suddenly and continuously throughout the immersion times. These processes resulted in an alteration in both physical and chemical coating properties. After 56 days, the coating remained on PEEK surfaces and the Ca/P ratio was 1.16. These results indicate that HA-TiN coating via pulsed DC magnetron sputtering followed by hydrothermal treatment improved the bioactivity of materials and provided a potential benefit to orthopedics and dental applications.