Solar-driven thermochemical splitting of CO2 and H2O using the redox properties of ceramic oxides is a promising option for the massive production of synthetic fuels without greenhouse gas emission and with complete recycling of chemical intermediates. The development of relevant redox oxides pairs with optimum formulation and design is a real challenge for the implementation of this attractive energy production technology. Redox oxide pairs offering both high redox properties and easy shaping ability have thus to be identified. In this work a series of (La,Sr)(Mn,X)O3 and (La,Ca)(Mn,X)O3 powders with X= Al, Mg, Ga or Cr have been prepared by Pechini-derived methods. In particular the impact of the synthesis parameters and type of dopant (X) on the physicochemical characteristics and reactivity of the powders (sinterability and redox properties) has been investigated. The results offer a relevant control over the synthesis / structure / properties relationships of the perovskite powders as crucial parameters targeting both the best perovskite formulations and design to be possibly integrated in solar thermochemical reactors.