This paper describes the results from multidisciplinary characterization/scattering techniques used for the quantitative characterization of industrial thermal barrier coating (TBC) systems used in advanced gas turbines. While past requirements for TBCs primarily addressed the function of insulation/ life extension of the metallic components, new demands necessitate a requirement for spallation resistance/strain tolerance, i.e., prime reliance, on the part of the TBC. In an extensive effort to incorporate these TBCs, a design-of-experiment approach was undertaken to develop tailored coating properties by processing under varied conditions. Efforts focusing on achieving durable/high-performance coatings led to dense vertically cracked (DVC) TBCs, exhibiting quasi-columnar microstructures approximating electron-beam physical-vapor-deposited (EB-PVD) coatings. Quantitative representation of the microstructural features in these vastly different coatings is obtained, in terms of porosity, opening dimensions, orientation, morphologies, and pore size distribution, by means of small-angle neutron scattering (SANS) and ultra-small-angle X-ray scattering (USAXS) studies. Such comprehensive characterization, coupled with elastic modulus and thermal conductivity measurements of the coatings, help establish relationships between microstructure and properties in a systematic manner.