Normal lyotropic liquid crystals (in the lamellar or hexagonal phases) are investigated as a route to afford a structured, three-dimensional, quasi-biphasic framework within which electron transfer cascades may be initiated voltammetrically. For model systems, we show that these can take place through reagent partitioning between the hydrophobic and hydrophilic subphases, and illustrate how the structure and its orientation, the nature of the ionic doping of the framework, and the hydrophobicity of the redox analyte may give rise to changes in the observed voltammetric waveshape. For the case of an artificial mimic of the first few stages of Photosystem I, we demonstrate that photo-induced electron transfer is likewise affected by the orientation, and develop a system of photon efficiency of similar to 0.1%. (C) 2012 Elsevier Ltd. All rights reserved.