Porcelain (veneer layer)/alumina (core layer) is a typical dental crown structure. Due to its high incidence of failure, a new porcelain/mullite (buffer layer)/alumina trilayer structure is designed, fabricated, and evaluated. Alumina green bodies were prepared by gel-casting process, and then calcined at 900 and 1100°C to infiltrate mullite precursor slurry of silica-rich (Al2O3·2SiO2) composition into the bodies. Porosity in the bodies is not dependent on calcination temperature, resulting in a similar infiltration depth. Porcelain was coated on the alumina sintered at 1600°C with and without mullite buffer layer. There are no delamination or cracks observed after firing the layered materials. Rod type microstructure and continuous composition are indicated at the interface in the case of the layered structure with mullite buffer layer. To investigate the cracking resistance behavior for this new structure, Vickers indentation and Hertzian contact fatigue tests were conducted. Cracks do not penetrate the interface with mullite buffer layer into the porcelain, showing a reversal case for the layered structure without mullite buffer layer. The layered structure with mullite buffer layer shows higher critical load for fracture than that without mullite buffer layer. Fracture mode of the layered structures in cyclic fatigue shows a top layer (porcelain) fracture at relatively low load (P = 250 N) and higher cycles (n = 106), and a bottom layer (alumina) fracture at higher load (P = 300 N) and relatively low cycles (n = 105).