A scheme of a glucose dehydrogenase-based bioelectrocatalytical system where ferricyanide is converted to ferrocyanide in the presence of highly reactive organic electron transfer compounds is investigated digitally. Glucose dehydrogenase (GDH) is highly reactive towards organic electron acceptors compared to the low reactivity of GDH with inorganic electron acceptors. In this bioelectrocatalytical scheme, the enzyme efficiently catalyzes biocatalytical conversion of an organic mediator, which is followed by the fast chemical cross reaction of the product in the presence of ferricyanide excess. By changing input parameters a special emphasis was directed towards the influence of the kinetic constants and reagents concentration on the sensitivity of the bioelectrode. The digital simulation of the system confirmed that the high sensitivity of the bioelectrode achieved in the presence of organic mediators is due to the synergistic substrates conversion demonstrated experimentally. in (Electroanalysis, 2012 (24) 273-277). (C) 2014 Elsevier Ltd. All rights reserved.