A systematic study which reveals the low thermal conductivity and high thermopower on a series of natural superlattice structures in the form BaXFCh (X: Cu, Ag, Ch: S, Se, Te), LaXSO (X: Cu, Ag) and SrCuTeF are presented. Low thermal conductivity is predicted by combining elastic constants and few well established models. The electronic properties reveal the highly two dimensional nature of band structure in the valence band, and this is confirmed through effective mass calculations. The huge difference in effective mass along different crystallographic directions in valence band introduces anisotropy in the transport properties for hole doping, and ‘a’ axis is found to be more favourable. In addition to these, the parameter A (S2σ/τT/κe/τ), which can decouple the relaxation time is also calculated, and it reveals the possibility of good thermoelectric properties in these compounds. Our results are comparable with prototype thermoelectric materials, and show better values than traditional TE materials. © 2017 Elsevier Ltd