The near-atomic thickness and natural molecular techniques, together with natural semiconductors and polymer-enabled hybrid heterostructures, of two-dimensional transition steel dichalcogenides (2D-TMDs) can modulate their optoelectronic and transport properties outstandingly. On this overview, the present understanding and mechanism of the newest and important 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 overview encompasses up-to-date gadget 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 overview offers insights into the synthesis of 2D-TMDs and natural layers, overlaying 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 section engineering, is introduced. The latest developments in 2D-TMDO-based optoelectronic synaptic gadgets, together with numerous 2D-TMDs and natural supplies for neuromorphic functions are mentioned. The part assesses their compatibility for synaptic gadgets, revisits the working rules, and highlights the latest gadget demonstrations. Present challenges and potential options are mentioned. Lastly, the overview concludes by outlining the present challenges that span from synthesis intricacies to gadget functions, and by providing an outlook on the evolving area of rising TMDO heterostructures.