We employ an electrospinning technique to precisely modulate nanofibers diameter by varying humidity, impacting surface morphology, roughness and frictional contact-area of triboelectric materials. This leads to an augmentation of surface charge density, promoting generation of surface charges on triboelectric materials. MXene (MX) and cellulose acetate (CA) form an effective pairing, with optimized sample CA-40_MX-40 at 40 % RH displaying five-fold increase in voltage compared to CA-20_MX-20. This sample achieves a peak power density of 2351.1 mW/m2 at 106 Ω, capable of powering LEDs. These findings introduce a viable fabrication technique to manipulate surface roughness, promising significant avenue for sustainable high-performance TENGs.