Composite materials based on III-VI elements are promising in designing efficient photoelectronic devices, such as thin film organic-inorganic solar cells. In this work, TlSe composite materials were synthesized on a model polymer polyamide using temperature and pH controlled adsorption-diffusion method via (a) selenization followed by (b) the exposure to the group III metal (Tl) salt solution and their surface morphological, chemical and crystalline phase information was determined with particular focus on their corresponding structure-optical property relationship. XRD analysis yielded a complex crystalline phase distribution which correlated well with the optical and surface morphological properties measured. pH 11.3 and 80 degrees C yielded well defined, low structural disorder composite material surface. After annealing in N-2 at 100 degrees C, polycrystalline PA-T1(x)Se(y) composite materials yielded a single TlSe phase due to the enhanced diffusion and reaction of thallium ions into the polymer. The method described here can be used to synthesize variety of binary III-VI compounds diffused into the polymer at relatively low temperatures and low overall cost, thus providing for a flexible synthesis route for novel composite solar energy harvesting materials. (C) 2014 Elsevier B.V. All rights reserved.