High-performance thermoelectric materials lie at the heart of thermoelectrics, the simplest technology applicable to direct thermal-to-electrical energy conversion. In its recent 60-year history, the field of thermoelectric materials research has stalled several times, but each time it was rejuvenated by new paradigms. This article reviews several potentially paradigm-changing mechanisms enabled by defects, size effects, critical phenomena, anharmonicity, and the spin degree of freedom. These mechanisms decouple the otherwise adversely interdependent physical quantities toward higher material performance. We also briefly discuss a number of promising materials, advanced material synthesis and preparation techniques, and new opportunities. The renewable energy landscape will be reshaped if the current trend in thermoelectric materials research is sustained into the foreseeable future.