Polyethylene terephthalate (PET) is widely used in various applications due to its excellent mechanical properties and chemical resistance. However, PET fibers still lack specific features and functionalities that can be improved via nano-additives, particularly metal oxides. In this study, we investigate the effect of adding TiO2 nanoparticles to PET to form PET/TiO2 fibers and examine their opto-mechanical properties. This study utilizes optical interferometric techniques to assess how mechanical stretching influences the optical and mechanical properties of PET fibers treated with TiO2 nanoparticles. A Mach–Zehnder interferometric setup, integrated with a versatile device capable of mechanically stretching samples, is used to achieve this task. Variations in refractive index and birefringence along the longitudinal axis of undrawn and drawn PET/TiO2 fibers are examined. The research meticulously explores the fluctuations and spatial variations in the refractive index and birefringence properties, exhibiting anisotropy in optical behavior, along the longitudinal axis of unstretched and stretched PET/TiO2 fibers. The findings and outcomes derived from this comprehensive study provide substantive information that can facilitate the enhancement and optimization of the coupled optical and mechanical properties of materials explicitly engineered for advanced applications.