Developing sintering and carbon resistant tar removal catalysts is crucial for biomass gasification technology. Herein, for the first time, NiCo@NiCo phyllosilicate@CeO2 hollow core shell catalysts have been designed for steam reforming of toluene (SRT) as the biomass tar model compound. They show both good catalytic activity and stability within 45 h of time on stream due to their high sintering resistance of NiCo because of the strong interactions between NiCo and CeO2, high metal exposure as a result of the high specific surface area, high surface metal concentration as well as the high oxygen vacancies as evidenced from the H-2-Temperature-programmed reduction (H-2-TPR), H-2 chemisorption and X-ray photoelectron spectroscopy (XPS) characterizations respectively. Additionally, the synergistic effect between Ni and Co further improves their carbon resistant property. By comparison, Co@Co phyllosilicate@CeO2 catalysts perform the lowest toluene conversion and stability mainly due to their structural instability during reaction resulting from their high Si/Co ratio, leading to their low specific surface area and Co exposure. The outstanding SRT performance of NiCo@NiCo phyllosilicate@CeO2 catalysts indicates their promising application for steam reforming of biomass tar reaction.