The quality of NiTi coating influences the thermal, microstructural, and mechanical behavior of the material produced by plasma spraying. To understand the behavior of the coating, the study has been designed and planned at two different plasma powers with various feed rates. NiTi as shape memory layers emerge as promising protective coatings on the surface of substrates against corrosion or wear. In the present investigation, NiTi multilayers were produced by thermal plasma spraying using NiTi (50 at. %) powder as the feedstock material. This work illustrates the studies of the microstructure, porosity of the coating layers, phase detection, hardness values, shape memory behavior, and the formation of samples produced by different spraying parameters. The porosity within coating layers has been analyzed based on the various shape factors of pores that correlate with the hardness and mechanical behavior of the samples. This work will explore the quality of the coating in terms of its porosity and compactness, which will affect the performance of the shape memory behavior. The functional coating of NiTi will have a significant influence on the durability of the material’s performance against corrosion.