This chapter focuses on the use of rigid phosphonic acids as precursors of hybrid materials. It first summarizes the usual methods employed for the synthesis of rigid phosphonic acid (phosphonic acid group directly bonded to an aromatic ring), which is a key stepped in designing original organic precursors and consequently original hybrids. Then, the method and experimental procedure to produce hybrid materials are summarized. The chapter illustrates hybrids obtained from polyphosphonic acid derivatives (homo‐polyfunctional precursors) and, subsequently, hetero‐polyfunctional precursors. It compares the structure of the hybrids obtained from different region isomers, and addresses the question of chemoselectivity when hetero‐polyfunctional precursors are employed as organic substrates. For some organic precursors, the consequences of changing the metallic precursor upon the structure of the hybrid are also reported. Finally, the chapter focuses on the use of a heteroaromatic unit as a rigid platform, and illustrates some recent applications.