The propagation characteristics and temperature coefficients of frequency characteristics of boundary waves, which concentrate the acoustic energy in the interface between the thin film-metal electrode and piezoelectric substrate using the structure of multithin film layers/metal electrode/piezoelectric substrates, are described. The new boundary waves are obtained by using higher velocity thin film as the top surface than internal ones of metal electrode and thin film. The materials with structures of AlN, Al2O3/SiO2/Al, Cu, Ag, Au/rotated Y-XLiNO3, and LiTaO3 are applied. The range of existence of boundary wave for thicknesses of thin films, electrodes on Y-XLiNbO3, LiTaO3, and temperature coefficient of frequency are shown. Experimental results of surface acoustic wave resonators show a good frequency response of admittance at 500 MHz range.