We succeeded in the deposition of piezoelectric thin film on a titanium substrate and on nickel-titanium alloy (shapememory alloy) by employing the hydrothermal synthesis method for the direct deposition of PZT thin film, which is a piezoelectric material, on a titanium substrate. The formed film is quite thin (tens of micrometers), and the density is low (theoretical density of ~70%). As the thin piezoelectric film is formed by the layering of many crystals, it is capable of responding to large deformations (up to 5%), which would have been inconceivable with the existing piezoelectric materials without any structural damages. The hydrothermal synthesis method was used in this research study to form films of PZT piezoelectric films on the surfaces of nickel-titanium shape-memory alloy wires to fabricate and evaluate a new multifunctional device that features a combination of four effects, namely, the shape-memory effect, super-elasticity effect, piezoelectric effect, and pyroelectric effect. The fabricated fiber was subjected to a tensile test in the super-elastic state, and the amount of deformation thereof was read from the piezoelectric effect to show the functioning of both the super-elastic effect and the piezoelectric effect.