Abstract Shuler, Aris & Tsuchiya (1972) have recently considered the combined effects of diffusive resistance and electrostatic field on the rate of reaction catalyzed by an enzyme immobilized on a non-porous surface. They employed a potential distribution for the electrical double layer which is asymptotically valid when surface potential is small.The complete Gouy-Chapman solution, which is valid for higher surface potential, is employed here. Numerical values of the effectiveness factor calculated with this potential distribution agree very closely with the results of Shuler et al. for most cases. It is shown that the effectiveness factor can (i) attain magnitudes much greater than unity in physically realizable systems, (ii) approach the solution for “infinite” surface potential at reasonable values of surface charge density, and (iii) pass through a maximum as bulk substrate concentration is varied. This behavior leads to the existence of an optimum surface concentration for enzyme immobilized on a highly charged non-porous support such that the most effective catalytic action on a charged substrate is ensured. Finally, it is established that significant electrical and/or diffusive effects result in non-linear Lineweaver-Burk plots of reciprocal observed reaction velocity against reciprocal bulk substrate concentration. These non-linear plots cannot be interpreted in the same way as linear plots obtained when enzyme is unbound.