In this study, composite thermoplastic polyurethane (TPU)/polystyrene (PS) nanofiber web and TPU nanofiber web and PS-extracted TPU/PS microfiber web have been experimentally investigated with regard to sound absorption and thermal conductivity coefficients to observe a potential use in sound and thermal insulation areas. Moreover, other properties such as surface area, morphology, tensile strength/elongation, air permeability, and thermal degradation have been analyzed. It has been observed that nanofiber web properties such as fiber diameter, extensibility, pore volume, and porosity have been clearly changed by Soxhlet extraction of PS from the composite TPU/PS nanofibers. PS-extracted TPU/PS fibers can be preferred for the low frequency (600–800 Hz) due to higher SAC (0.7). On the other hand, TPU nanofibers were more effective at medium frequencies (around 3000 Hz, SAC 0.6). Both TPU and PS-extracted TPU/PS composite fibers had similar thermal conductivities, whereas TPU/PS composite nanofibers had lowest thermal conductivity (0.05 W/mK) with moderate maximum SAC value (around 1000 Hz, SAC 0.5–0.6).