Utilization of advanced engineering thermoplastic materials in fused filament fabrication (FFF) 3D printing process is critical in expanding additive manufacturing (AM) applications. Polypropylene (PP) is a widely used thermoplastic material, while silicon dioxide (SiO2) nanoparticles (NPs), which can be found in many living organisms, are commonly employed as fillers in polymers to improve their mechanical properties and processability. In this work, PP/SiO2 nanocomposite filaments at various concentrations were developed following a melt mixing extrusion process, and used for FFF 3D printing of specimens’ characterization according to international standards. Tensile, flexural, impact, microhardness, and dynamic mechanical analysis (DMA) tests were conducted to determine the effect of the nanofiller loading on the mechanical and viscoelastic properties of the polymer matrix. Scanning electron microscopy (SEM), Raman spectroscopy and atomic force microscopy (AFM) were performed for microstructural analysis, and finally melt flow index (MFI) tests were conducted to assess the melt rheological properties. An improvement in the mechanical performance was observed for silica loading up to 2.0 wt.%, while 4.0 wt.% was a potential threshold revealing processability challenges. Overall, PP/SiO2 nanocomposites could be ideal candidates for advanced 3D printing engineering applications towards structural plastic components with enhanced mechanical performance.