The triblock copolymer PEO-PPO-PEO is thermoresponsive and have demonstrated excellent properties to act as a reducing as well as capping agent for synthesis of metal nanoparticles. Effect of reaction temperature in growth, morphology and chemical properties of self-assembled structures of silver PEO -PPO-PEO nanocomposites on silicon substrates is described here. The polymer-metal composites are deposited on hydrophilic and hydrophobic silicon substrates through adsorption from solution at different temperatures. Morphologies of the nanocomposite films observed by SEM are strongly dependent on reaction temperature as well as on philicity/phobicity of silicon substrates. Detailed investigations of the chemical properties of nanocomposite materials are performed using XPS and NEXAFS. At lower reaction temperatures, mainly thermoresponsive behavior of the copolymer controls nanocomposite formation and their organization on the substrates. Whereas at higher reaction temperatures, chemical nature of the copolymer that directly take part in the reaction is changed drastically and alters the nanocomposite formation process as well as the nature of self-assembly. The resemblance in spectroscopic data of this modified/degraded copolymer with that of fatty acid molecules indicate formation of fatty acid-like molecules at higher temperature. (C) 2013 Elsevier S.V. All rights reserved.