Polycarbonate/acrylonitrile butadiene styrene (PC/ABS) blends are widely used as engineering plastic alloys; however, they have a low fire safety level. To improve the flame-retardant property of PC/ABS, a zirconium-based metal-organic framework material (UiO-66) was synthesized with zirconium chloride and terephthalic acid and used as a flame-retardant cooperative agent. Its flame-retardant performance and mode of action in the PC/ABS blends were carefully investigated. The results showed that UiO-66 had good thermal stability and delayed the pyrolysis of the materials, thus significantly enhancing the efficiency of intumescent flame retardants. By compounding 7.0 wt% hexaphenyloxy-cyclotri-phosphazene (HPCTP) with 3.0 wt% UiO-66, the PC/ABS blends reached a limiting oxygen index value of 27.0% and V0 rating in the UL-94 test, showing significantly improved resistance to combustion dripping. In addition, UiO-66 enhanced the smoke and heat suppression characteristics of the intumescent flame-retardant materials. Finally, the flame-retardant mode of action in the blends was indicative of UiO-66 having a cooperative effect on the flame-retardant performance of PC/ABS/HPCTP materials. This work provides good ideas for further development of the flame-retardant ABS/PC.