To promote the efficiency of waste heat recovery from granulated blast furnace (BF) slag, a novel method of catalyst-enhanced steam reforming of bio-oil to recover heat from slag is proposed. CaO is utilized as a superior catalyst for the process of catalyst-enhanced steam reforming. The thermodynamic production of the catalyst-enhanced steam reforming of bio-oil in granulated BF slag is obtained using HSC 6.0 software. The optimal conditions are mainly assessed according to the hydrogen yield, hydrogen concentration and carbon production. Through the thermodynamic production and industrial application, the temperature of 608 °C, S/C of eight and pressure of 1 bar are found as the optimal conditions. At the optimal conditions, the hydrogen yield, hydrogen concentration and carbon production are 95.25%, 76.89% and 0.28 mol/kg, respectively. Taking the temperature of 625 °C, S/C of eight and pressure of 1 bar as an example, the catalyst could improve the hydrogen yield and hydrogen concentration from 93.99% and 70.31% to 95.15% and 76.49%, respectively. It is implied that utilizing the catalyst could promote the hydrogen yield and hydrogen concentration of steam reforming of bio-oil to recover waste heat from granulated BF slag. The mechanism of catalyst-enhanced steam reforming of bio-oil to recover waste heat from granulated BF slag is obtained to guide the subsequent industry application.