The invention relates to a non-aluminium zeolite molecular sieve containing a TON / MTT skeleton topology structure and a preparation method of the zeolite molecular sieve. The preparation method comprises the steps of dissolving an inorganic alkaline source by using deionized water, then adding a template agent A, a boron source, an iron source or a gallium source, dissolving completely, then adding a template agent B or a silicon source, and adding an-all silicon ZSM-22 molecular sieve as seed crystal into obtained initial gel and then performing ultrasound; utilizing microwave radiation to heat a mixture subjected to the ultrasound so as to obtain a non-aluminum zeolite molecular sieve with a TON / MTT composite topology structure after crystallization. According to the method, the non-aluminium zeolite molecular sieve replaced with a heteroatom is utilized, the acidity is moderate, and the multilevel acidity distribution is adjustable; by adopting the preparation method provided by the invention, the synthesis time is short, the miscellaneous crystal is less, the particle size is uniform, and the repeatability is good. The composite molecular sieve has a huge potential application value in the aspects such as hydrocracking and isomerization.