This review presents the up-to-date knowledge collected on the redox and electron transfer (ET) properties of cytochrome c (cyt c) attached to biomimetic organic films on electrodes with the aid, of surface-enhanced resonance Raman scattering (SERRS). Strategies to attach the cyt c to alkanethiol, self-assembled monolayers (SAMs) coated metals (Ag and Ag/Au hybrids) are described. General, features of SER(R)S spectroscopy and conditions for conducting a meaningful electrochemical SERRS (EC-SERRS) experiment are highlighted. Structural information on SAM and tethered cyt c envisaged with SER(R)S is discussed. A great effort is made to demonstrate a key role of substrate selection, when collecting and comparing SERRS and electrochemical data. Influence of biomimetic linker on structure, orientation and electronic properties of immobilized cyt c is discussed. A principle of probing heterogeneous ET with time-resolved (TR) potential-jump SERRS is explained. Conclusions concerning the mechanism of the ET for cyt c attached to alkanethiol SAM coated gold provided by the insight with SERRS spectroscopy are presented. A special attention is paid to the discussion of the effect of the electric field provided by alkanethiol SAM on protein ET properties and biological function. (C) 2013 Elsevier Ltd. All rights reserved.