The influence of unit cell geometric parameters on the thermal fracture behavior and thermal shock resistance of honeycomb ceramics sandwich structures is revealed for the first time. The present study establishes a continuum model for the thermal fracture of sandwich structures, and a discrete numerical representation model for the equivalent fracture toughness of honeycombs, respectively. A novel evaluation approach for the thermal shock resistance of porous material structures has been provided by combining the two models. The effects of temperature dependence, face sheet thickness, honeycomb orientation and honeycomb geometrical parameters on thermal shock resistance are studied. Results indicate that changing the inclined angle of honeycomb can effectively increase the critical thermal shock temperature rise. Auxetic honeycomb sandwich structures with the inclined angle of −9° can reach the peak of the critical temperature rise. The results would contribute to the application of honeycomb sandwich structures in thermal protection systems.