The hydrolysis acidification process is an economical and effective method, but its efficiency is still low in treating azo dye wastewater. It is therefore crucial to find more suitable and efficient means or techniques to further strengthen the process of treating azo dye wastewater by a hydrolytic acidification process. In this study, a hydrolytic acidification aerobic reactor was used to simulate the azo dye wastewater process. The change of wastewater quality during the reaction process was monitored, and the deep enhancement effect of single or composite biological intensification technology on the treatment of azo dye wastewater by the hydrolytic acidification process was also explored. Co-substrate strengthening and the addition of fructose co-substrate can significantly improve the efficiency of hydrolytic acidification. Compared with the experimental group without the addition of fructose, the decolorization ratio of wastewater was higher (93%) after adding fructose co-substrate. The immobilization technology was strengthened, and the immobilized functional bacteria DDMZ1 pellet was used to treat the simulated azo dye wastewater. The results showed that the composite technology experimental group with the additional fructose co-matrix had a better decolorization efficiency than the single immobilized bio-enhancement technology, with the highest decolorization ratio of 97%. As a composite biological intensification method, the fructose co-matrix composite with immobilized functional bacteria DDMZ1 technology can be applied to the treatment of azo dye wastewater.