A novel synthesis route to the high-silica zeolite MCM-22, which includes the combined use of a flexible, linear diquaternary ion N,N,N,N',N',N'-hexamethyl-1,5-pentanediaminium and Na+ or K+, is described. Unlike the previously known organic structure-directing agents leading to the crystallization of MCM-22 and related materials, the organic additive used here E was found to locate inside both the 12-ring supercages and the sinusoidal 10-ring channels of MWW topology.