In this short communication, TiO2-nanoparticle-functionalized biodegradable polylactide (PLA) nonwoven scaffolds with a superhydrophobic and superadhesive surface are reported regarding their water immobilization, antibacterial performance, and deodorization. With numerous regular oriented pores on their surface, the as-fabricated electrospun porous PLA/TiO2 composite fibers possessed diameters in the range from 5 µm down to 400 nm, and the lengths were even found to be up to the meters range. The PLA/TiO2 composite fiber surface was demonstrated to be both superhydrophobic and superadhesive. The size of the pores on the fiber surface was observed to have a length of 200 ± 100 nm and a width of 150 ± 50 nm using field-emission scanning electron microscopy and transmission electron microscopy. The powerful adhesive force of the PLA/TiO2 composite fibers toward water droplets was likely a result of van der Waals forces and accumulated negative pressure forces. Such a fascinating porous surface (functionalized with TiO2 nanoparticles) of the PLA/TiO2 composite fiber scaffold endowed it with multiple useful functions, including water immobilization, antibacterial performance, and deodorization.