Multilayer thin film reference materials for the sputter depth profiling analysis are used to calibrate the sputter depth scale by measuring the sputtering rate and to optimize the sputtering conditions for the best depth resolution. Surface analysis group of Korea Research Institute of Standards and science (KRISS) have developed various types of multilayer thin films by using an ion beam sputter deposition and in-situ surface analysis system. The chemical states of the thin films reference materials were certified by in-situ XPS and the thicknesses were certified by transmission electron microscopy (TEM).