A new approach to the fabrication of Langmuir-Blodgett molecular arrays containing multiredox centres has been investigated. In this work, the compounds studied incorporate covalently-linked ferrocene and tetrathiafulvalene moieties, but no ’traditional’ alkyl chain. The behaviour of these materials, at the air/water interface, in pure form and mixed with long-chain fatty acids, is reported. In the condensed region of the surface pressure vs. area isotherm, the areas per molecule are shown to depend on the proportion and nature of the fatty acid. Monolayer and multilayer films have been built-up on solid supports and the electrochemical properties of these layers studied using cyclic voltammetry. The results suggest a preferential orientation of the ferrocene groups, and are in marked contrast to those obtained from cast films of the same compounds.