Zr65Al7.5Ni10Cu12.5Pd5 bulk metallic glasses (BMGs) in various relaxation states were prepared under different cooling rates. The grain growth rate of the primary quasicrystal was examined near the crystallization temperature. It was approximately 1 × 10-9 m/s in less relaxed BMGs and approximately twice as large in relaxed BMGs. In contrast, the calculated homogeneous nucleation rate of the less relaxed samples was five to ten times higher (5 × 1019–1 × 1020/m3s) than those in the relaxed BMGs. The results indicate that the relaxation state of glassy alloys has a marked effect on nucleation and grain growth behaviors.