The rising demand for wireless electronics and sustainable energy solutions drives the search for alternatives to conventional batteries. Triboelectric nanogenerators (TENGs) offer a promising route by converting mechanical energy into electricity via frictional events between two different material surfaces. Here, a simple and scalable surface modification method using conventional laser printing was applied to investigate the effect on triboelectric performance of cellulose-based materials against polytetrafluoroethylene (PTFE). Regenerated cellulose (RC) and cellulose acetate (CA) films were print patterned with black toner in a conventional laser printer at different surface coverages from 0% to 100%. The measured power output for RC films against PTFE showed minimal response from the patterning over the whole range and could be considered as constant with an average of 52 ± 2 W m−2. On the other hand, the CA sample films showed a significant and gradual increase in power output from 45 to 65 W m−2 as the toner print coverage increased from 0% to 100%. These results demonstrate that synergistic interactions between the printed toner and the substrate can strongly influence TENG performance and are highly dependent on the physical and chemical properties of the underlying material. In CA, toner–substrate intermixing enabled by laser printing temperatures exceeding the glass transition temperature provides a proof-of-concept for enhancing triboelectric performance through controlled surface–bulk interactions.