Magic-sized nanoclusters (MSCs) have been attracting enduring interest by virtue of the quantum confinement effect, discrete energy band structure, and enriched catalytic active sites. Nevertheless, up to date, exploration of MSCs artificial photosystems and fine-tuning of spatial vectorial charge transfer in photoredox catalysis have so far been scarcely reported. Hence, we employed a facile and easily accessible layer-by-layer (LbL) assembly strategy to highly ordered, alternately, and periodically deposit oppositely charged tailor-made transition metal chalcogenides (TMCs) MSCs and non-conjugated polymer (NCP) building blocks on the MO substrate, resulting in the MO/(NCP-TMCs MSCs)