We report on the preparation of Ga/Al nanoalloys embedded glass-ceramic by heat treatment as well as femtosecond laser irradiation. The Ga/Al nanoalloys embedded glass-ceramic exhibits intense extinction in the visible region, as well as superior optical nonlinearities. The third-order nonlinear optical properties of the glass-ceramics were investigated by employing Z-scan technique. The maximum nonlinear extinction coefficient β and nonlinear refraction γ value reached 1.14 × 10−11 m/W and 2.01 × 10−17 m2/W, respectively. Three-dimensional Ga/Al nanoalloys embedded structures were also achieved in glass by scanning the focused femtosecond laser beam. These results may find applications for the fabrication of ultrafast optical switches and diffractive optical elements.