The constructing of van der Waals heterostructures and the ornament of 2D supplies with natural molecules share a standard purpose: to acquire ultrathin supplies with tailor-made properties. Performing managed chemistry on van der Waals heterostructures would add an additional degree of complexity, offering a pathway in the direction of 2D 2D-0D mixed-dimensional heterostructures. Right here we present that thiol-ene-like “click on” chemistry can be utilized to brighten franckeite, a naturally occurring van der Waals heterostructure with maleimide reagents. ATR-IR and NMR analyses corroborate the Michael addition mechanism through the formation of a S–C covalent bond, whereas Raman and HR-TEM present that the SnS2-PbS alternating construction of franckeite is preserved, and counsel that SnS2 reacts preferentially, which is confirmed by way of XPS. We illustrate how this system can be utilized so as to add useful molecular moieties by adorning franckeite with porphyrins. UV-vis-NIR spectroscopy confirms that the chromophore floor state stays operative, exhibiting negligible ground-state interactions with the franckeite. Excited-state interactions throughout the hybrid interface are revealed. Time-resolved photoluminescence confirms the presence of excited-state de-activation within the linked porphyrin ascribed to vitality switch to the franckeite.