Surfactants have been extensively used in electrode modification for electroanalysis in recent years. In this review we highlight dihexadecylphosphate (also known as dicetylphosphate, dihexadecyl hydrogen phosphate, DHP), which is a hydrophobic surfactant molecule with a negatively charged polar head located at a phosphate group on one side of the molecule, linked to two long hydrocarbon chains (two long hydrophobic tails) on the other side. DHP has been used in association with other electroactive nanomaterials such as carbon nanotubes, gold nanoparticles, and/or graphene in sensing and biosensing. In this paper, we present an overview of the use of DHP in the modification of electrode surfaces. In the course of the paper, we first introduce DHP, followed by an overview of its applications in electrochemical sensors and biosensors. The prospects and future applications of DHP in the field of electrochemistry are also evaluated.