Distributed sensing has been an attractive alternative to the traditional single-point sensing technology when measurement at multiple locations is required. Traditional distributed sensing methods based on silica optical fiber and electric coaxial cables have some limitations for specific applications, such as in smart textiles and wearable sensors. By adopting the fiber thermal drawing technique, we have designed and fabricated multi-material electrode-embedded polymer fibers with distributed sensing capabilities. Polymers sensitive to temperature and pressure have been incorporated into the fiber structure, and thin metal electrodes placed inside fiber by convergence drawing have enabled detection of local impedance change with electrical reflectometry. We have demonstrated that these fibers can detect temperature and pressure change with high spatial resolution. We have also explored the possibility of using polymer optical fiber in a Raman scattering based distributed temperature sensing system. Stokes and Anti-Stokes signals of a PMMA fiber illuminated by a 532 nm pulsed laser was recorded, and the ratio was used to indicate local temperature change. We have also developed a unique way to fabricate porous polymer by thermal drawing polymer materials with controlled water content in the polymer. The porous fibers were loaded with a fluorescent dye, and its release in tissue phantoms and murine tumors was observed. The work has broadened the scope of multi-material, multi-functional fiber and may shed light on the development of novel smart textile devices.