Porous hybrid materials and MOF (Metal–Organic-Framework) films represent modern designer materials that exhibit many requirements of a near ideal and tunable future thermoelectric (TE) material. In contrast to traditional semiconducting bulk TE materials, porous hybrid MOF templates can be used to overcome some of the constraints of physics in bulk TE materials. These porous hybrid systems are amenable for simulation and modeling to design novel optimized electron-crystal phonon-glass materials with potentially very high ZT (figure of merit) numbers. Porous MOF and hybrid materials possess an ultra-low thermal conductivity, which can be further modulated by phonon engineering within their complex porous and hierarchical architecture to advance the TE figure of merit (ZT). This Perspective review discusses recent results of MOF TE materials and provides a future outlook and the vision to the search for the next generation TE porous hybrid and MOF materials, which could be part of the green renewable energy revolution with novel materials of sustainably high ZT values.