In this white paper, it will be demonstrated that the use of three HILIC phases, which provide very different and complementary selectivity to one another, is both practical and effective for HILIC method development. These selectivity differences can be exploited, together with mobile phase pH, to thoroughly explore selectivity and to enable selection of an appropriate stationary phase/mobile phase combination during HILIC method development. A systematic, step-by-step approach to method development is recommended to make it easier for chromatographers to develop new HILIC methods in a productive manner.