The strategies to enhance electron transfer rates between redox-active, light-harvesting molecules attached to semiconductor surfaces and redox mediators in solution by modifying molecular structure are not fully investigated yet. Therefore, the design of molecules with controlled electron transfer rates remains a challenge. The aims of this work are to quantify the effect of long alkyl chain substitution on the electron transfer from cobalt(II/III) tris(2,2′-bipyridine) to organic molecules containing carbazole and thiophene and to demonstrate that alkyl chains can be used to enhance electron transfer between donor-acceptor pairs. To this end, we study the effect of using a combination of donor and acceptor molecules with and without alkyl chains on electron transfer kinetics. Using transient absorption spectroscopy, we show that when only the molecules or the mediators have long alkyl chains, electron transfer is slightly blocked as expected. Counterintuitively, electron transfer is up to 13 times faster when long alkyl chains are attached to both the redox-active molecules and the redox mediators. The faster electron transfer is explained by an alkyl-alkyl chain interaction between the donor/acceptor, leading to the proximity (trapping) of the redox mediators close to the π-conjugated backbone of the molecules. These results suggest that intermolecular interactions can be used to enhance the electron transfer rates significantly even with well-established insulating alkyl chains attached to molecules without changing the electrochemical driving force.