The present paper reports novel outcome comprising experimental results on electromagnetic interference (EMI) shielding and radar signal absorption characteristics of one-dimensional (1D) TiO2/SiO2 core-shell nanofibers. 1D TiO2/SiO2 core-shell nanofibers with various concentrations of nanoparticles (NPs) were fabricated using a single-nozzle co-electrospinning method. The core-shell structure of polyvinylpyrrolidone/polyacrylonitrile nanofibers with NPs have been electrospun from the homogeneous solution of polyvinylpyrrolidone (PVP and TiO2 NPs, as core) and polyacrylonitrile (PAN and SiO2 NPs, as shell). The morphologies and structures of TiO2/SiO2 core-shell nanofibers were characterized by XRD, FTIR, EDS, and SEM images. Microwave absorption properties of the synthesized nanofibers were studied using a vector network analyzer between 2 and 20 GHz at room temperature. The maximum EMI-shielding effectiveness of 150 dB is obtained with the dominant shielding mechanism of absorption of EM radiation. The excellent microwave absorption properties of the composites nanofibers are attributed to the special 1D fibrous structure and the effective dielectric loss.