Sustained increase in plastic use has placed a significant burden on waste disposal infrastructure. Pyrolysis is the process of decomposing high-molecular-weight compounds by heating waste plastics at 500–1000 °C without oxygen. This process considerably reduces greenhouse gas emissions and has a high alternative energy effect (0.57 TOE ton−1). After a separation process, the oil produced by pyrolysis (C5–C20) can yield naphtha oil (C6–C7). Subsequently, hydrogen can be produced through a reforming reaction of this naphtha oil. Here, we produced hydrogen from waste plastic pyrolysis oil over a Ni/Ce-Zr-Mg/Al2O3 catalyst using a steam reforming process. A model oil combining the major substances of C6 and C7 (hexane, hexene, heptane, heptene, and toluene) was formed. From the reaction products, the hydrogen yield was obtained based on analysis of H2, CO, and CO2 concentrations using gas chromatography. The effect of N2 and O2 addition on hydrogen yield was analyzed within a temperature range of 750–850 °C, steam/carbon (S/C) ratio of 0.6–4, and space velocity of 7600–19,100 h−1. In addition, a durability test was performed using 3 wt.% Ni/Ce-Zr-Mg/Al2O3 catalysts for 100 h; a hydrogen yield of 91.3% was maintained from the refined waste plastic oil.