This paper considers the state-of-the-art and open scientific and technological questions in thermoelectric materials and devices, from phonon engineering and scattering methods, to new and complex materials and their thermoelectric behavior. The paper also describes recent approaches to create structural and compositional material systems designed to enhance the thermoelectric figure of merit and power factors. We also summarize and contextualize recent advances in the use of superlattice structures and porosity or roughness to influence phonon scattering mechanisms and detail some advances in integrated thermoelectric materials for generators and coolers for thermally stable photonic devices.