TiO2/MgO core-sheath structured nanofibers (NFs) were fabricated through co-electrospinning (i.e., coaxial electrospinning), and then the long TiO2/MgO NFs were converted into short TiO2/MgO nanorods (NRs) by ultrasonic treatment. Based on the TiO2/MgO NRs, two novel technical textiles, that is, a photovoltaic smart textile integrating flexible dye-sensitized solar cells and a photocatalytic functional textile immobilizing photocatalyst, were developed. The effect of the insulating MgO sheath on the semiconducting TiO2 core was discussed. Compared with the pure TiO2 NR counterparts, the TiO2/MgO NR-based photovoltaic and photocatalytic textiles exhibit better performances. The common reason for the performance enhancements is that the charge recombinations occurring in both photovoltaic and photocatalytic processes are greatly suppressed when TiO2 is coated by MgO. Finally, the potential applications of these two types of textiles were proposed. This work offers a unique insight into the development of special textiles through the combination of new energy and environmental technologies and traditional textile research.