CdS is a promising visible-light-driven photocatalyst, but it is highly toxic. Therefore, exploring alternatives that minimize toxicity while maintaining its photocatalytic properties is crucial. Carbon allotropes have been suggested as eco-friendly scaffolds for making high-performance photocatalysts with a small amount of toxic but visible light-responsive CdS additive to reduce environmental risk. However, it is unclear how small amounts of CdS in the nanocomposite can avoid a threat to environmental safety, and the role of surface functional groups on the physical interfaces for photocatalysis has not been sufficiently elucidated. Here, we used OH-functionalized carbon nanotubes (CNT-OH) as a support for CdS nanoparticles (NPs) and investigated the effect of CdS loading on photocatalytic activity and toxicity. Comprehensive microscopy coupled with machine learning-assisted spectroscopy revealed that electronic structure alterations occur uniquely at heterojunctions where CdS NPs contact CNT-OH, uncovering them as being catalytically active. Notably, the CNT-OH loaded by only 3 wt% CdS NPs resulted in a highly enhanced photocatalytic activity comparable to pure CdS NPs for selective oxidation of 2,5-hydroxymethylfurfural and degradation of 4-chlorophenol. These findings provide insight into heterocontact engineering using visible light-responsive catalysts and functionalized platforms to develop environmentally benign photocatalysts with high performance.