Heat dissipation is a critical bottleneck for microelectronic device performance and longevity. At micrometer and nanometer length scales heat carriers scatter at the boundaries of the material reducing its thermal conductivity. Additionally, thermal boundary conductance across dissimilar material interfaces becomes a dominant factor due to the increase in surface area relative to the volume of device layers. Therefore, techniques for monitoring spatially varying temperature profiles, and methods to improve thermal performance are critical to future device design and optimization. The first half of this thesis focused on frequency domain thermoreflectance (FDTR) to measure thermal transport in nanometer-thick polymer films and across an organic-inorganic interface. Hybrid structures of organic and inorganic materials are widely used in devices such as batteries, solar cells, transistors, and flexible electronics. The Langmuir-Blodgett (LB) technique was used to fabricate nanometer-thick polymer films ranging from 2 - 30 nm. FDTR was then used to experimentally determine the thermal boundary conductance between the polymer and solid substrates. The second half of the thesis focused on developing a fundamental understanding of thermal transport in wide-bandgap (WBG) materials, such as GaN, and ultrawide-bandgap (UWBG) materials, such as diamond, to improve thermal dissipation in power electronic devices. Improvements in WBG materials and device technologies have slowed as thermal properties limit their performance. UWBG materials can provide a dramatic leap in power electronics technologies while temporarily sidestepping the problems associated with their WBG cousins. However, for power electronic devices based on WBG- and UWBG-materials to reach their full potential the thermal dissipation issues in these hard-driven devices must be understood and solved. FDTR provides a comprehensive pathway towards fully understanding the physics governing phonon transport in WBG- and UWBG-based devices. By leveraging FDTR imaging and measuring samples as a function of temperature, defect concentration, and thickness, in conjunction with transport models, a well-founded understanding of the dominant thermal-carrier scattering mechanisms in these devices was achieved. With this knowledge we developed pathways for their mitigation.