The interactions of dendrimers having a phosphorus atom at each branching point, of type poly(phosphorhydrazone) (PPH), with different types of materials based on silicon and aluminum are reviewed. These dendrimers can be used for the functionalization of solid surfaces at the nanoscale, either by covalent immobilization, or by electrostatic interactions, especially for constructing perfectly controlled multi‐layers by layer‐by‐layer (LbL) deposit. The properties of such hybrid materials as chemical sensors, as very sensitive biological sensors, as well as substrates for the growing of cells are described. The PPH dendrimers can also be embedded inside materials. The resulting hybrid materials have been used for the capture of pollutants, in particular CO 2 in air and chromate and methylene blue in waste water.