The thermotropic phase behavior of phthalocyanines (Pcʼs) with eight oligo(ethylene oxide) alkoxy side chains has been investigated. An increase in the number of ethylene oxide units results in a decrease in the solid-to-mesophase and isotropization temperatures. The investigated compounds display a discotic hexagonally ordered (D ho ) mesophase. The solubilization of LiI/I 2 into the polar side chains of the Pcʼs has been studied both in solution and in spin-coated films, and the effect on the aggregate formation is discussed. At higher temperatures, the Pc -LiI/I 2 complex is not stable and small crystallites are formed. The dark direct current conductivity of these films is reported as a function of LiI/I 2 concentration in the polar side groups of the Pcʼs. The observed decrease in conductivity with increasing salt concentration is related to the morphology of the material.