Recently, triboelectric nanogenerators (TENGs) have been widely utilized to address the energy demand of portable electronic devices by harvesting electrical energy from human activities or immediate surroundings. To increase the surface charge and surface area of negative TENGs, previous studies suggested several approaches such as micro-patterned arrays, porous structures, multilayer alignment, ion injections, ground systems and mixing of high dielectric constant materials. However, the preparation processes of these nanocomposite TENGs have been found to be complex and expensive. In this work, we report a simple, efficient and inexpensive modification of poly(dimethylsiloxane) (PDMS) using graphene nanoplatelets (GNPs) fillers and a Na2CO3 template. This GNP-PDMS was chemically bonded using 3-aminopropylethoxysilane (APTES) as a linker with an electrode multilayer made by layer-by-layer deposition of polyvinyl alcohol (PVA) and poly(4-styrene-sulfonic acid) (PSS)-stabilized GNP (denoted as [PVA/GNP-PSS]n). A 33 wt.% Na2CO3 and 0.5 wt.% of GNP into a PDMS-based TENG gives an open-circuit voltage and short-circuit current density of up to ~270.2 V and ~0.44 μA/cm2, which are ~8.7 and ~3.5 times higher than those of the pristine PDMS, respectively. The higher output performance is due to (1) the improved surface charge density, 54.49 μC/m2, from oxygen functional moieties of GNP, (2) high surface roughness of the composite film, ~0.399 μm, which also increased the effective contact area, and (3) reduced charge leakage from chemical bonding of GNP-PDMS and [PVA/GNP-PSS]3 via APTES. The proposed TENG fabrication process could be useful for the development of other high-performance TENGs.