Wollastonite coatings were deposited on Ti6Al4V substrate at the substrate temperatures of room temperature, 200 °C, 400 °C and 600 °C by the atmosphere plasma spraying, respectively. The effect of substrate temperature on the microstructure, phase composition, mechanical properties and dissolution behavior of wollastonite coatings were investigated. The microstructure and phase composition of coatings were examined by SEM and XRD. The hardness and elastic modulus were obtained by the Knoop indentation tests. In addition, the dissolution behavior of coatings was evaluated by immersion in SBF solution. The results indicate that a slight decrement of porosity and an obvious increment of crystallinity were found with the substrate temperature. The hardness and elastic modulus of coatings increased with the substrate temperature up to 400 °C firstly, and then a decrement was observed with the temperature further increasing to 600 °C. The dissolution rate of coatings characterized by the pH changes and the released Ca, Si and P concentration in the SBF decrease with the substrate temperature, which is related to the porosity and crystallinity of coatings. It is revealed that through increasing the substrate temperature during plasma spraying is a feasible method to improve the mechanical properties and to decrease the dissolution of wollastonite coatings.