This experimental study presents tribological characteristics under boundary lubrication contacts associated with electrorheolocal (ER) fluid. ER fluid is prepared by using phosphorated starch particles and silicone oil. Experimental apparatus of tribological tester is designed and constructed to evaluate tribological characteristics of pin specimens. Wear tests under boundary lubrication of ER fluid are experimentally performed under consideration of several operational factors such as normal load, sliding distance, sliding speed and specimen materials: steel, copper and aluminum. After wear test, microscopic surface changes of the worn pin specimens are analyzed in order to investigate measured wear characteristics by using the scanning electron microscope (SEM) as well as surface profilometer. In addition, the chemical wear characteristics are investigated by using energy dispersive x-ray spectroscopy (EDS). Moreover, friction coefficient measurements under different materials of pin specimens are conducted for the tribological investigations. In order to verify the effect of starch phosphate particles in ER fluid, the wear test results with ER fluid are compared with test results with only silicone oil. The results clearly present that the phosphorated starch based ER fluid shows the stabilized wear as well as friction characteristics after run-in operations, but the wear rate under ER fluid is increased.