Nowadays, using a polymeric membrane ion-selective electrode (ISE) to achieve reliable ion sensing in complex samples remains challenging because of electrode fouling. To address this challenge, we describe a polymeric membrane ISE with excellent anti-fouling and self-cleaning properties based on surface covalent modification of an anatase TiO 2 coating. Under ultraviolet illumination, the reactive oxygen species produced by photocatalytic TiO 2 can not only kill microorganisms but also degrade organic foulants into carbon dioxide and water, and a formed superhydrophilic film can effectively prevent the adsorption of foulants, thus inhibiting the occurrence of biofouling and organic fouling of the sensors. More importantly, residual foulants could be fully self-cleaned through the flow of water droplets. By using Ca 2+ -ISE as a model, an anti-fouling polymeric membrane potentiometric sensor has been developed. Compared to the unmodified electrode, the TiO 2 -coated Ca 2+ -ISE exhibits remarkably improved anti-biofouling properties with a low bacterial adhesion rate of 4.74% and a high inhibition rate of 96.62%. In addition, the proposed electrode displays unique properties of anti-organic dye fouling and a superior self-cleaning ability even after soaking in a concentrated bacterial suspension of 10 9 CFU mL -1 for 60 days. The present approach can be extended to improve the fouling resistance of other electrochemical or optical membrane sensors and is promising for the construction of contamination-free sensors.