Ultrasonochemically driven graphene oxide (GrO) functionalization (f) with sulfanilamide (SA) near-edge catalyzed heterogeneous graphene oxide (h-GrO) as economic scalable f-(SA)GrO is reported. The novel in situ H₂O association was subsequently aligned towards C–O–C active sites of GrO and f-(SA)GrO surfaces on a mechanistic HO˙ release with efficient sonothermocatalysis. Compared to GrO, the electronic bandwidth of heterogeneous f-(SA)GrO structure is reduced from 4.00 to 3.67 eV at 280 nm excitation. The contribution of heteroatoms (-N) of f-(SA)GrO at near-edges could have a greater bandwidth efficacy due to synergistic effect. The composition-driven structural alignments with near-edges have been investigated with synchrotron radiation soft X-ray absorption spectroscopy and high-resolution X-ray photoelectron spectroscopy. Efficient photoluminescent bandwidth structures at 3.67 and 1.87 eV for f-(SA)GrO and 4.00, 2.04 and 1.46 eV for GrO with their corresponding surface quantized electronic density contour images, photon flux, and power density were investigated. Sonothermocatalysis efficiencies for methylene blue (MB) by GrO and f-(SA)GrO sonocatalysts at regular time intervals up to 60 min are 68.68 to 83.05% and 81.44 to 87.31% respectively. Distorted sonothermocatalysis efficiencies for rhodamine B (RhB) are 43.71 to 61.38% and 47.7 to 53.39% respectively. The sonocatalyst f-(SA)GrO is thermodynamically more efficient (>85%) in MB sonothermocatalysis than GrO. Ultrasound time driven temperatures exhibited a thermal progression of sonothermocatalysis for MB and RhB degradation. It generated activation energy (E_a), frequency factor (A), enthalpy (ΔH), entropy (ΔS), and Gibbs energy (ΔG), which depict an oxidative radical degradation. Interdependence of ΔH, ΔS, and ΔG implies a contribution of SA vis-a-vis activation energy (0.489 and 0.342 J mol⁻¹ for MB and 0.234 and 0.075 J mol⁻¹ for RhB degradation) on an Arrhenius scale. The functional groups of sonocatalysts were restored after sonothermocatalysis of MB, detected from Fourier-transform infrared spectra and diffraction patterns, confirming their reusability.