The solid-state electrochemistry and thermochromism of cobalt hexacyanoferrate (CoHCF) in a composite matrix comprising silica sol-gel and generation-4 poly(amidoamine) dendrimer was investigated and compared to analogous studies of CoHCF powders. The thermochromic behaviour over the range, 25-85 degrees C, of the reduced form in the sol-gel matrix differed from that of the powder. The results suggested that even in the presence of KCl in this matrix, the dominate form of the reduced CoHCF was (Co2FeII)-Fe-II(CN)(6) rather than (K2CoFeII)-Fe-II(CN)(6). In contrast, the thermochromic behaviour of the oxidized form of CoHCF was the same as that reported for the powders. The observed cyclic voltammetric behaviour of CoHCF in the sol-gel composite matrix was the same as that of powders in terms of the electrode processes, but the influence of scan rate on the current was dependent upon the cell configuration. With the CoHCF-doped composite contacted to a solution phase, this behaviour was consistent with anion intercalation/de-intercalation control, but in a solid-state cell, a transition from a surface-controlled to a mass-transport controlled current was observed. (C) 2005 Elsevier Ltd. All rights reserved.