Recently, double perovskite-based oxide materials have been proposed for thermoelectric (TE) applications due to their environment-friendly nature, high-temperature stability, better oxidation resistance, and lower processing cost compared to conventional chalcogenides and intermetallics. In this review article, we have comprehensively summarized our recent research studies on Sr2B′B″O6-based double perovskites for high-temperature TE power generation. We have shown that decoupling of phonon-glass and electron-crystal behavior is possible in oxides by reducing thermal conductivity due to induced dipolar glassy state as a result of relaxor ferroelectricity. We have also introduced metal-like electrical conductivity (∼105 S/m) in these ceramics that are inherently insulator in nature. Moreover, we have observed interesting behavior of temperature-driven p–n type conduction switching assisted colossal change in thermopower in some of these oxides, hitherto, obtained only in chalcogenides. The charge transport mechanism in these complex oxides has been analyzed by small polaron hopping conduction model in conjugation with defect chemistry.