Bioactive glass-ceramic coatings have great potential in dental and orthopedic medical implant applications, due to its excellent bioactivity, biocompatibility and osteoinductivity. However, most of the coating preparation techniques either produce only thin thickness coatings or require tedious preparation steps. In this study, a new attempt was made to deposit bioactive glass-ceramic coatings on titanium substrates by the liquid precursor plasma spraying (LPPS) process. Tetraethyl orthosilicate, triethyl phosphate, calcium nitrate and sodium nitrate solutions were mixed together to form a suspension after hydrolysis, and the liquid suspension was used as the feedstock for plasma spraying of P2O5-Na2O-CaO-SiO2 bioactive glass-ceramic coatings. The in vitro bioactivities of the as-deposited coatings were evaluated by soaking the samples in simulated body fluid (SBF) for 4 h, 1, 2, 4, 7, 14, and 21 days, respectively. The as-deposited coating and its microstructure evolution behavior under SBF soaking were systematically analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD), inductively coupled plasma (ICP), and Fourier transform infrared (FTIR) spectroscopy. The results showed that P2O5-Na2O-CaO-SiO2 bioactive glass-ceramic coatings with nanostructure had been successfully synthesized by the LPPS technique and the synthesized coatings showed quick formation of a nanostructured HCA layer after being soaked in SBF. Overall, our results indicate that the LPPS process is an effective and simple method to synthesize nanostructured bioactive glass-ceramic coatings with good in vitro bioactivity. Crown Copyright (C) 2010 Published by Elsevier B.V. All rights reserved.