Melt-spun Nd9.5Fe81Zr3B6.5 ribbons were prepared by the melt-spinning technique. The phase evolution and magnetic properties were studied by X-ray diffraction, differential scanning calorimetry, transmission electron microscopy observations, and magnetization measurements. It is indicated that melt spinning at different wheel velocities caused the as-quenched ribbons to have distinctive structure. The phase transformation of the ribbons during annealing takes place in two steps: α-Fe transforms from the amorphous phase firstly, followed by formation of Nd2Fe14B phase. With increasing the initial quenching rate, the microstructure of optimally heat treated ribbons becomes coarser, which results in the weakening of the exchange coupling effect between the hard and soft phase. This leads to drastic deterioration of magnetic properties of annealed ribbons with increasing the initial quenching rate.