One kind of novel biodiesel waste cooking oil ethyl ester (WCOEE) was prepared via transesterfication reaction between waste cooking oil and ethanol. The tribological behavior of diesel/WCOEE blend was evaluated with a four-ball tribometer. The wear resistance, extreme pressure, and friction reduction of the blend were improved with increasing WCOEE. The optimal content of WCOEE in the blend was 20 vol%. It was also found that free fatty acids (FFAs) had a positive effect on the wear resistance of blend. The lubrication improvement of the blend was ascribed to the formation of polyester film and high polarity of fatty acid ethyl ester.