We report on the generation of Smart hybrid functional surfaces via a novel surface functionalization pathway termed as Surface Grown Hybrid Functional Layers or SgL, which competes with the conventioanl Layer-by-Layer (LbL) approach. In SgL approach, the smart surfaces were generated in a single step at a fluid/solid interface through fine tuning of electro-static interaction between the stable oppositely charged building blocks (BBs) as a function of the ionic strength of the dispersion. Admixing of the oppositely charged BBs at high ionic strength resulted a dormant solution, where the elctrostatic interaction is completely switched off The complexation between the BBs can be triggered by switching back on the interaction via a controlled removal of salt (desalting) by dialysis or dilution with water yield a reactive solution. The onset of this desalting transition at a given substrate enabled the fabrication of smart hybrid layers with unique morphology, properties and applications.