The urgent need for sustainable energy supply requires maximum exploitation of renewable energy sources. The latter, being of intermittent nature, need to be coupled with efficient energy storage. Solar-thermal power-plants are inherently compatible with thermal storage, which is a cost-efficient method of storing energy for later use but the field is currently dominated by sensible heat molten salts used as heat storage media but with a maximum operating temperature of about 560oC. Certain ceramic materials, able to induce reversible reduction-oxidation reactions under air flow, are promising alternatives to molten salts because they can withstand much higher temperatures (>1000oC) and thus can be integrated with high-efficiency air-Brayton thermodynamic cycles. At the same time the chemical energy stored/released during such reduction-oxidation reactions can boost energy storage density by up to 10 times cf. sensible only concepts. In this framework, Ca-Mn-based perovskite compositions were demonstrated to function effectively as energy storage materials. The current work offers insights on material synthesis parameters to achieve relatively high purity Ca-Mn-based compositions and subsequently optimize their redox performance in the course of a preliminary 5-cycle campaign. Moreover, the occurring structural transitions and their corresponding heat effects are also discussed and elaborated upon. This study is the first step towards the, currently in progress, process of synthesising – at multi kg scale – and shaping these compositions into extruded honeycomb-like monolithic structures for subsequent future application in lab- and pilot-scale high temperature thermochemical energy storage systems.