The promotional effect of Zn was investigated relative to the calcining activation of HZSM-5. It was found that the lignin separated from walnut shell could be liquefied into small molecular ethers such as anisole by the promotional effect of the modified catalyst. Experimental results showed that, after the loading of Zn, the HZSM-5 catalyst retained its original crystal structure, which exhibited good metal dispersion. Besides, due to the existence of two interactions respectively of Zn with Al and Zn with a Brønsted-Lowry acid on the Zn/HZSM-5 catalyst surface, the remaining catalyst intergranular distance increased, particularly for the 2% Zn/HZSM-5 catalyst. The inside of the catalyst was in a state of spherical particle aggregation with a narrow pore size distribution and uniform particle size. The peak intensity of the Si-O stretching vibration was affected by the content of Zn, which was least affected for the 2% Zn/HZSM-5 catalyst. The signal peak of this small molecule ether was not found in the absence of the metal ions, and the catalytic effect of 2% Zn/HZSM-5 was more distinct. Calculated by the mass difference method, the yield of the liquid via the 2% Zn/HZSM-5 catalyst was 59.8%, including phenol and small molecule ethers represented by anisole.