The rapid solidification behavior of Co-Sn alloys was investigated by melt spinning method. The growth morphology of αCo phase in Co-20%Sn hypoeutectic alloy changes sensitively with cooling rate. A layer of columnar αCo dendrite forms near the roller side at low cooling rates. This region becomes small and disappears as the cooling rate increases and a kind of very fine homogeneous microstructure characterized by the distribution of equiaxed αCo dendrites in αCo3Sn matrix is subsequently produced. For Co-34.2%Sn eutectic alloy, anomalous eutectic forms within the whole range of cooling rates. The increase of cooling rate has two obvious effects on both alloys: one is the microstructure refinement, and the other is that it produces more crystal defects to intensify the scattering of free electrons, leading to a remarkable increase of electrical resistivity. Under the condition that the grain boundary reflection coefficient r approaches 1, the resistivity of rapidly solidified Co-Sn alloys can be predicted theoretically.