Shape memory alloy coating on an optical fiber plays an important role in developing novel active thermal sensors in the field of microelectromechanical systems. In this article, a detailed analysis of NiTi alloy deposited over plastic optical fiber was discussed. A detailed investigation of the morphological, structural, and thermal properties of the NiTi-coated optic fiber was conducted. The uniformity, crystallinity, transformation temperatures, and thermal stability of the coatings were measured using differential scanning calorimetry, scanning electron microscopy, X-ray diffraction, and thermogravimetric analysis, respectively. Also, an electrical actuation setup thermo-mechanical test was conducted through Joule heating in which different voltages at varying loads have been used. The sensor characteristic–based parameters (time response and sensitivity) were also calculated. The article presents a complete analysis of experimental results showing the properties and performances of the plastic optical fiber after coating with shape memory alloy.