Bi2Sr2CaCu2Ox(Bi-2212) and Bi2Sr2Ca2Cu3Oy(Bi-2223) high-Tc superconductors(HTS) have been manufactured by plasma spraying, partial melt process(PMP) and annealing treatment(AT). A Bi-2212/2223 HTS coating layer was synthesized through the peritectic reaction between a 0212 oxide coating layer and 2001 oxide coating layer by the PMP-AT process. The 2212 HTS layer consists of whiskers grown in the diffusion direction. The Bi-2223 phase and secondary phase in the Bi-2212 layer were observed. The secondary phase was distributed uniformly over the whole layer. As annealing time goes on, the Bi-2212 phase decreases with mis-orientation and irregular shape, but the Bi-2223 phase increases because a new Bi-2223 phase is formed inside the pre-existing Bi-2212 crystals, and because of the nucleation of a Bi-2223 phase at the edge of Bi-2212 crystals by diffusion of Ca and Cu-O bilayers. In this study the spray coated layer showed superconducting transitions with an onset Tc of about both 115 K, and 50 K. There were two steps. Step 1 at 115 K is due to the diamagnetism of the Bi-2223 phase and step 2 at 50 K is due to the diamagnetism of the Bi-2212 phase.