Protein-film voltammetry (PFV) is a versatile tool designed to provide insight into the enzymes physiological functions by studying the redox properties of various oxido-reductases with suitable voltammetric technique. The determination of the thermodynamic and kinetic parameters relevant to protein's physiological properties is achieved via methodologies established from theoretical considerations of various mechanisms in PFV. So far, the majority of the mathematical models in PFV have been developed for redox proteins undergoing a single-step electron transfer reactions. However, there are many oxido-reductases containing quinone moieties or polyvalent ions of transition metals like Mo, Mn, W, Fe or Co as redox centers, whose redox chemistry can be described only via mathematical models considering successive two-step electron transformation. In this work we consider theoretically the protein-film redox mechanisms of the EE (Electrochemical-Electrochemical), ECE (Electrochemical-Chemical-Electrochemical), and EECat (Electrochemical-Electrochemical-Catalytic) systems under conditions of cyclic staircase voltammetry. We also propose methodologies to determine the kinetics of electron transfer steps by all considered mechanisms. The experimentalists working with PFV can get large benefits from the simulated voltammograms given in this work. (C) 2012 Elsevier Ltd. All rights reserved.