Thin films of TiO2 (anatase) nanoparticles are assembled at an electrode surface via a layer-by-layer deposition process employing phytic acid, pyromellitic acid, or flavin adenine dinucleotide (FAD) as molecular binders. With all three types of binders, layers of typically 30 nm thickness are formed each deposition cycle. FAD as an electrochemically active component immobilized at the surface of the TiO2 particles is reduced to FADH(2) and reoxidized in a chemically reversible two electron-two proton redox process. Two distinct voltammetric signals are observed for the immobilized FAD redox system associated with (i) hopping of electrons at the TiO2 surface (reversible) and (ii) conduction of electrons through the TiO2 assembly (irreversible). The conduction of electrons through the TiO2 assembly is possible by diffusion over considerable distances as well as through a "spacer" layer of TiO2 phytate. An order of magnitude (upper limit) estimate for the diffusion coefficient of electrons through TiO2 phytate, D-electron approximate to 10(-6) m(2) s(-1), is obtained from voltammetric data. Finally, it is demonstrated that the calcination of TiO2 assemblies causes dramatic changes in the electron transfer kinetics for the immobilized FAD/FADH(2) redox system.