Engineering of materials with high dielectric constant is of great importance for highly efficient TENGs. The feasible way to reach this is to compose it with proper chemicals having a high dielectric constant such as nanopowders. In this work, the doping effect of the two different architectures of the same compound on triboelectric production has been studied. Nanopowder Cerium Oxide (CeO2) and its fiber arrangement have been selected and embedded into the silicon to enhance the tribonegative charge potential and their contributions to TENGs’ parameters relying on the varying doping ratios have been investigated. A large spectrum of analyses, such as XRD, SEM, TEM, HR-TEM, EDX, elemental mapping, Raman spectrum with mapping, optical microscope, and profilometer, has been used to elucidate the relationship between structural properties of produced dielectric layers and device performance. Both CeO2 nanoparticles and nanofibers, at 5wt% doping rates, have provided in turn ∼80% and ∼63% times higher power than that of undoped form since their doping has delivered a formation of more effective surface area. The findings of this research play an important role in addressing the issue of how TENGs’ performance can be regulated by playing with materials’ architecture instead of its chemical composition.