In this work, a transparent and high strength spinel glass-ceramics containing excess Al2O3 (26.5 mol%) were prepared successfully. The influence of the substitution amount of TiO2 by ZrO2 on the structure, nucleation process, crystallization behavior and properties of glasses and glass-ceramics were investigated respectively. The results showed that ZrO2 would play different roles under different concentrations and the existence form of Al in glass network would also be influenced. Moreover, the nucleation process and crystallization behavior of glasses were studied and the mechanism of TiO2/ZrO2 induced crystallization was proposed. It is concluded that TiO2/ZrO2 as nucleating agents can induce glass to form Ti-rich phase droplets or Zr-rich inhomogeneous regions. Finally, the properties of the glasses and glass-ceramics with different nucleating agents were compared and analyzed. It is found that high Al2O3 content contributes to the improvement of microhardness, and could strengthen the role of ZrO2 in refining grains.