The aim of this paper is to investigate the influence of non-isovalent alkali (Li, Na, K, and Cs) substitution in Bi2Sr2CaCu2O8, in particular on its synthesis conditions and on their resistive and thermopower electrical properties. Liquid phase development during the synthesis process leads to the formation of sintered materials at a lower temperature compared to the undoped 2212 compound. The final composition is discussed as a function of which crystallographic site is partially substituted. The presence of alkali ions in the initial chemical composition leads to improved electrical properties. Such data are correlated with the microstructure and chemical composition of the end-product.