The main objective of this work was the production of novel polyvinylpyrrolidone/diacid modified Mg‐substituted fluorapatite (DM‐MFA) nanocomposites (NC)s, by sonication process. Mg‐substituted fluorapatite (MFA) powders with a chemical composition of Ca9.5Mg0.5(PO4)6F2 were prepared by mechanical alloying technique. Initially, surface of MFA was modified by bioactive chiral diacid monomer, N‐trimellitylimido‐l‐leucine as a coupling agent to form DM‐MFA nanoparticles. DM‐MFA NPs were utilized as a filler, to give the NCs with potential bioactivity. Examination of transmission electron microscopy (TEM), and field emission scanning electron microscopy (FE‐SEM) microphotographs displayed that, there is no aggregation of a large quantity of particles. The above NCs showed rather improved thermal stability compared with pure polymer. The improvement of thermal behavior was related to the uniform and good dispersion of DM‐MFA in the polymer matrix as well as the strong hydrogen bonding between CO of PVP and OH of DM‐MFA. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44254.