Herein, we showcase an effective strategy to develop multifunctional nanocomposite materials that can serve as an excellent NIR-reflective, high refractive index and anticorrosive coatings. A series of multifunctional nanocomposite coatings of TiO2/Poly(thiourethane-urethane)-urea are developed and evaluated for their performance. TiO2 nanoparticles (TiNPs) are grafted with a sulfur-rich hyperbranched polyol (SHBP) to impart surface functionalization and active participation in network formation. Each stage of modifications are followed with detailed characterizations employing H-1/C-13-NMR, mid-FTIR, ESI-MS for structural elucidations of the targeted compositions while TGA, DSC, DMTA, TEM, FE-SEM are employed for assessing thermal, mechanical and morphological properties of the modified TiNPs and cured hybrid coatings. The UV-Vis-NIR studies and ellipsometry results revealed that these coatings exhibited notable NIR-reflectance (similar to 90%) which is hitherto undocumented for such materials. Coupled with appreciable transmittance in the visible region and high refractive index (>1.6) at 550 nm they demonstrate good optical properties. Additionally, anticorrosion performance of these coatings evaluated under corrosive conditions displayed a significant corrosion resistance, similar to 10(-6) mm per year. The findings of this study suggest the success in amalgamating multiple properties in one composition by tailoring the architecture of the polymer-nanohybrid matrix. (C) 2017 Elsevier Ltd. All rights reserved.