Highly substituted potato starch phosphate (HPSP) particles were synthesized via an esterification process of potato starch with a mixture of several different concentrations of disodium hydrogen phosphate and sodium hydrogen phosphate. These particles were characterized via thermogravimetric analysis, scanning electron microscope, and inductively coupled plasma mass spectrometer. The electrorheological (ER) fluid was prepared by dispersing these HPSP particles in nonconducting silicone oil, and their ER properties were investigated. The HPSP particle-based ER fluid exhibited typical ER responses with a nonzero yield stress under an applied electric field. We examined the yield stresses for the potato starch-based anhydrous ER system by varying the degree of phosphate substitution and found that the higher polarization induced by the external electric field strength resulted in the higher values of yield stresses and shear stresses.