Wollastonite-based bioceramic powders were synthesized by solid-state reaction between calcite and silica powder. To control the phase and bioactivity of wollastonite, we also prepared four kinds of wollastonite-based bioceramics by adding an enstatite (MgSiO3) powder. After solid state reaction at 1000-1300 degrees C, micron-sized powders were obtained by milling and screening. By using these powders, wollastonite coatings were fabricated on zirconia substrates by a room temperature spray process, and their microstructure and composition under different coating condition were investigated. Wollastonite coatings on zirconia substrates were formed with the homogeneous microstructure and nanoscaled grain size. The phase composition of the resultant wollastonite coatings was similar to that of the starting powders, however, the grain size of the wollastonite particles was reduced to about 100 nm due to their formation by particle impaction and fracture. The wollastonite coating layer exhibited bioactivity in a stimulated body fluid and forming ability of 25 nm sized-hydroxyapatite precipitates of during in vitro test in SBF solution.