The near-atomic thickness and natural molecular programs, together with natural semiconductors and polymer-enabled hybrid heterostructures, of two-dimensional transition metallic dichalcogenides (2D-TMDs) can modulate their optoelectronic and transport properties outstandingly. On this evaluate, the present understanding and mechanism of the newest and vital breakthrough of novel interlayer exciton emission and its modulation by harnessing the band power alignment between TMDs and natural semiconductors in a TMD/natural (TMDO) hybrid heterostructure are demonstrated. The evaluate encompasses up-to-date machine demonstrations, together with field-effect transistors, detectors, phototransistors, and photo-switchable superlattices. An exploration of distinct traits in 2D-TMDs and natural semiconductors delves into the functions of TMDO hybrid heterostructures. This evaluate offers insights into the synthesis of 2D-TMDs and natural layers, masking fabrication strategies and challenges. Band bending and cost switch by way of band power alignment are explored from each structural and molecular orbital views. The progress in emission modulation, together with cost switch, power switch, doping, defect therapeutic, and part engineering, is offered. The latest developments in 2D-TMDO-based optoelectronic synaptic units, together with numerous 2D-TMDs and natural supplies for neuromorphic functions are mentioned. The part assesses their compatibility for synaptic units, revisits the working ideas, and highlights the latest machine demonstrations. Current challenges and potential options are mentioned. Lastly, the evaluate concludes by outlining the present challenges that span from synthesis intricacies to machine functions, and by providing an outlook on the evolving subject of rising TMDO heterostructures.