Our work examines the structural-electronic correlation of a new curcuminoid, AlkCCMoid, as a dielectric material on different substrates. For this purpose, we show a homemade sublimation method that allows the direct deposition of molecules on any type of matrix. The electronic properties of AlkCCMoid have been evaluated by measurements on single crystals, microcrystalline powder, and sublimated samples, respectively. GIWAXS studies on surfaces and XRD studies on powder have revealed the existence of polymorphs and the effect that substrates have on curcuminoid organization. We describe the dielectric nature of our system and identify how different polymorphs can affect electronic parameters such as permittivity, all corroborated by DFT calculations. Display omitted •A new curcuminoid with triple bonds ending groups shows dielectric behavior•Direct sublimation of the curcuminoid on substrates is achieved under mild conditions•Structural-electronic correlation on surfaces is a strong analytical tool•Permittivity is greatly affected by polymorphism Chemistry; Crystallography; Supramolecular chemistry; Surface science