Templating methods provide an alternative approach for fabricating macroporous solids with three-dimensionally ordered arrays of pores with diameters from tens to hundreds of nanometers. The main goal of this work is the fabrication of thermoelectric-opal composite and inverse opals made of thermoelectric material in order to obtain enhanced performance by reducing the thermal conduction. Chemical bath deposition (CBD) has been employed and thermodynamic modelling was used to obtain optimum conditions for the desired phase of particle formation within the channels of the opal-like structures. The wetting behaviours of opals were considered in the choice of the appropriate solvents. When loading is finished, the precursor is decomposed and reduced when appropriate. The opal template is then removed by pyrolysis to obtain the macroporous structures. The structural properties of materials produced were investigated.