This review deals with the beneficial use of surfactants in various fields of electrochemistry, in general and in the modification of electrodes with immobilized electroactive species, in particular. Special emphasis is laid on the modification of electrodes with metal hexacyanoferrates (MHCFs). After an introduction and brief notes on fundamentals of surfactants, and their applications in electrochemistry, covering some of the very important works in the past two decades involving beneficial use of surfactants, the article gives a brief account on metal hexacyanoferrate modified electrodes and the salient features of our published results on the beneficial role of cetyltrimethylammonium bromide (CTAB), a cationic surfactant, in the modification of electrodes with MHCFs and their derivatized oxides, and with titanium dioxide.