Rapidly solidified Al 87 Ni 7Cu 3Nd 3 metallic glasses were prepared by using melt spinning. Its calorimetric behavior was characterized by using differential scanning calorimeter. The metallic glasses were partially crystallized under continuous heating regime. Primary crystallization was studied through structural characterization of the amorphous and partially crystallized ribbons by means of conventional X ray diffraction and transmission electron microscopy with selected area electron diffraction. The results show that, the as spun ribbons are fully amorphous and homogeneous on the micron scale, but contain high density of nanoscale quenched in clusters or crystallite embryos. Primary crystallization mainly leads to formation of two phase mixture of α Al nanocrystalline and residual amorphous phase. Precipitation of α Al nanoparticles is limited by build up and overlapped diffusion field of solute atoms with low diffusion rate. At the earlier stage of primary crystallization the crystal nuclei exhibit high density and growth rate. With the α Al crystal growing, the crystal growth rate decreases, and even at the later stage further crystallization into α Al crystal becomes difficult to occur due to thermal stabilization of the residual nickel and neodymium enriched amorphous phase, the saturated values of crystallized volume fraction and α Al crystal diameter getting to 20%30% and 515 nm. Rapidly solidified Al 87 Ni 7Cu 3Nd 3 metallic glasses were prepared by using melt spinning. Its calorimetric behavior was characterized by using differential scanning calorimeter. The metallic glasses were partially crystallized under continuous heating regime. Primary crystallization was studied through structural characterization of the amorphous and partially crystallized ribbons by means of conventional X ray diffraction and transmission electron microscopy with selected area electron diffraction. The results show that, the as spun ribbons are fully amorphous and homogeneous on the micron scale, but contain high density of nanoscale quenched in clusters or crystallite Primary crystallization mainly leads to formation of two phase mixture of α Al nanocrystalline and residual amorphous phase. Precipitation of α Al nanoparticles is limited by build up and overlapped diffusion field of solute atoms with low diffusion rate. At the earlier stage of prima ry crystallization the crystal nuclei exhibit high density and growth rate. With the α Al crystal growing, the crystal growth rate decreases, and even at the later stage further crystallization into α Al crystal becomes difficult to occur due to thermal stabilization of the residual nickel and neodymium enriched amorphous phase, the saturated values ​​of crystallized volume fraction and α Al crystal diameter getting to 20% 30% and 515 nm.