Recently, the conjugation of metal oxide nanoparticles with organic moieties has attracted the attention of many researchers for various applications. In this research, the green and biodegradable vitamin C was employed in a facile and inexpensive procedure to synthesize the vitamin C adduct (3), which was then blended with green ZnONPs to fabricate a new composite category (ZnONPs@vitamin C adduct). The morphology and structural composition of the prepared ZnONPs and their composites were confirmed by several techniques: Fourier-transform infrared (FT-IR) spectroscopy, field-emission scanning electron microscopy (FE-SEM), UV-vis differential reflectance spectroscopy (DRS), energy dispersive X-ray (EDX) analysis, elemental mapping, X-ray diffraction (XRD) analysis, photoluminescence (PL) spectroscopy, and zeta potential measurements. The structural composition and conjugation strategies between the ZnONPs and vitamin C adduct were revealed by FT-IR spectroscopy. The experimental results for the ZnONPs showed that they possessed a nanocrystalline wurtzite structure with quasi-spherical particles with a polydisperse size ranging from 23 to 50 nm, while the particle size appeared greater in the FE-SEM images (band gap energy of 3.22 eV); after loading with the L-ascorbic acid adduct (3), the band gap energy dropped to 3.06 eV. Later, under solar light irradiation, the photocatalytic activities of both the synthesized ZnONPs@vitamin C adduct (4) and ZnONPs, including the stability, regeneration and reusability, catalyst amount, initial dye concentration, pH effect, and light source studies, were investigated in detail in the degradation of Congo red dye (CR). Furthermore, an extensive comparison between the fabricated ZnONPs, composite (4), and ZnONPs from previous studies was performed to gain insights to commercialize the catalyst (4). Under optimum conditions, the photodegradation of CR after 180 min was 54% for ZnONPs and 95% for the ZnONPs@L-ascorbic acid adduct. Moreover, the PL study confirmed the photocatalytic enhancement of the ZnONPs. The photocatalytic degradation fate was determined by LC-MS spectrometry.