Electron velocity distribution obtained by direct spacecraft observation in space is contaminated by photoelectrons. The photoelectrons are generated due to the solar ultraviolet ray, and are regarded as artificial noise from a viewpoint of scientific research. We propose a method for separating photoelectron component from ambient electron component. Our method uses multivariate normal mixture model, whose parameters are determined via the Expectation-Maximization (EM) algorithm. Initial parameters of the EM algorithm are computed through the classification of the velocity space by a spherical surface of some arbitrary radius.