The present study describes the influence of potassium and hydroxyl substitutions on the structural, thermal and mechanical properties of fluorapatite bioceramics. A set of non-stoichiometric ion-substituted compounds, with a chemical formula of Ca10−xKx(PO4)6F(2−2x)(OH)x with 0 ≤ x ≤ 1 synthesized by the wet precipitation method, were found to be single-phase apatites crystallizing in the hexagonal P63/m space group. The structural parameters, as well as the crystallite sizes, increased accordingly to the amount of added dopant-ions. The thermal behavior of these compounds, studied within the temperature range 500–1200 °C, indicated a partial decomposition of the apatitic phase and its transformation to tricalcium phosphate β-Ca3(PO4)2 at temperatures exceeding 750 °C. A relative density of the sintered samples achieved the highest value with x = 0.25 and reached about 95% after sintering at 1050 °C for 1 h. The microstructures of the sintered samples were of a trans-granular aspect and experienced an increase in the radius of their pores as x increased. The prepared bioceramic materials were mechanically characterized by means of Young’s modulus, flexural strength and fracture toughness measurements. The overall trend of these parameters evolved comparably to the relative density, and the maximum values obtained for x = 0.25 were measured to be 96 MPa, 47 MPa and 1.14 MPa·m1/2, respectively.