The optoelectronic response of a material governs its suitability for a wide range of applications, from photon detection to photovoltaic conversion. To conquer the material limitations and achieve improved optoelectronic responses, nanotechnology has been employed to arrange subunits with specific size-dependent quantum mechanical properties in a hierarchically organized structure. However, building a functional optoelectronic system from nano-objects remains a formidable challenge. In this paper, the fabrication of a new artificially engineered optoelectronic material by the preferential growth of silicon nanocrystals on the bottom of the pore-channels of mesoporous silica is reported. The nanocrystals form highly stable interface structures bonded on one side; these structure show strong electron-phonon coupling and a ferroelectric-like hysteretic switching property. A new class of multifunctional materials is realized by invoking a concept that employs semiconductor nanocrystals for optical sensing and utilizes interfacial polar layers to facilitate carrier transport and emulate ferroelectric-like switching.