There is considerable current effort to discover new thermoelectric materials with a high figure of merit Z. Some of these new materials are narrow-gap semiconductors with rather complex crystal structures. In this paper we discuss the results of electronic structure calculations in two classes of such systems. The first class consists of BaBiTe3, a structural and chemical derivative of the well-studied Bi2Te3. Similarities and differences in the band structures of these two systems are discussed. The second class consists of half-Heusler or “stuffed”-NaCl compounds MNiX, where M is Y, La, Lu, Yb, and X is a pnictogen; As, Sb, Bi. To understand the physical reason behind the energy gap formation, we compare the electronic structure of YNiSb with that of an isoelectronic system ZrNiSn, another isostructural compound of thermoelectric interest. These calculations were carried out within density functional theory (in generalized gradient approximation) using self-consistent full-potential LAPW method. Energy gaps and effective masses associated with the conduction band minimum and valence band maximum have been calculated and these quantities have been used to estimate transport properties. Large room temperature thermopower values in Bi2Te3 and BaBiTe3 can be understood in terms of multiple conduction and valence band extrema whereas similar large values in ZrNiSn and other half-Heusler compounds can be ascribed to large electron and hole effective mass.