This paper explores the physicochemical and physicomechanical process occurring during the formation of dendrimeric fluorinated polysilsesquioxanes (PSSQ) coated over an active aluminum surface. The changes in chemical composition of PSSQ have been monitored as a function of time and investigated using FTIR 2D correlation spectroscopy. The percolation of water molecules, hydrogen bonding, and interference of several physicochemical processes occurring in curing and cross-linking reaction in PSSQ have been monitored. The changes in surface morphology as a function of time have been recorded with atomic force microscopy and correlated with the nanomechanical analyses through nano-indentation. Specifically, nanoscratch and wear resistances were recorded at various time intervals to understand the transformation in the surface characteristics of the material. The ultimate aim of this work was to understand the correlation between reacting ingredients, surface features, wear, and friction by applying a self-lubricated coating made of fluorinated PSSQover an aluminum surface. Attempts have been made to understand how the quantity and interaction of water molecules control the hydrolysis, condensation, and subsequent cross-linking reactions. The degree of cross-linking eventually controls the hardness and adhesion characteristics of the molecules, which in turn control the surface topology, resulting friction, wear resistance, and consequent surface life span of the material.