This study describes a method by which to synthesize SiO2-based graphene nanoballs (SGB) using atmospheric pressure chemical vapor deposition (APCVD) with copper vapor assistance. This method should solve the contamination, damage, and high costs associated with silica-based indirect graphene synthesis. The SGB was synthesized using APCVD, which was optimized using the Taguchi method. Multiple synthesis factors were optimized and investigated to find the ideal synthesis condition to grow SGB for thermoelectric (TE) applications. Raman spectra and FESEM-EDX reveal that the graphene formed on the silicon nanoparticles (SNP) is free from copper. The prepared SGB has excellent electrical conductivity (75.0 S/cm), which shows better results than the previous report. Furthermore, the SGB nanofillers in bismuth telluride (Bi2Te3) nanocomposites as TE materials exhibit a significant increment in Seebeck coefficients (S) compared to the pure Bi2Te3 sample from 109 to 170 μV/K at 400 K, as well as electrical resistivity decrement. This approach would offer a simple strategy to improve the TE performance of commercially available TE materials, which is critical for large-scale industrial applications.