Recent advancements in self-charging power devices highlight the potential of dielectric nanofillers in polymer matrixes to improve the performance of microsupercapacitor–triboelectric nanogenerator (TENG) integrated devices. However, achieving homogeneous dispersion of nanofillers into polymer matrixes remains a key bottleneck, often leading to inconsistent performance, reduced stability, and lower energy efficiency. This work presents an innovative chemical functionalization strategy covalently knitting MXene/graphene oxide (GO)/siloxene and MXene/reduced GO/siloxene networks into textile substrates, resulting in a consistent output performance and the development of a durable device. The single-electrode TENG delivered an output voltage of 380 V, a current density of 6.3 μA/cm2, a power density of 627 μW/cm2, and the transfer of 0.55 ± 0.03 μC of charge. The integrated device charged a voltage of 2.4 V after 110 s of continuous hand tapping, powering smart electronics. These results showcase the potential of chemically engineered heterostructures to address longstanding challenges in self-charging devices.