The discontinuous ordering (DO) reaction represents the mechanism of atomic ordering in alloys at such low temperatures, at which the mobility of atoms in the bulk of the alloy can be neglected and the ordering process occurs only in the regions swept by migrating grain boundaries (GBs). In order to study the relationship between the grain boundary crystallography and the kinetics of the DO reaction in the Fe-50 at.% Co alloy, the orientations of all the grains in a 8x4 mm 2 sample have been determined in the scanning electron microscope by an automated analysis of the backscattered Kikuchi patterns, and the crystallographic orientation image of the sample has been constructed. With the help of this image, completed by a light microscopy map of the sample, all GBs have been numbered sequentially and the maximal width of the ordered phase has been determined in the light microscope (LM) for each individual GB. Afterwards, the misorientation parameters for all GBs investigated in the LM have been determined (totally 226 GBs). Such a procedure allowed us to establish a relationship between the rate of the DO reaction at individual GBs and their misorientation parameters. The data are presented as the dependencies of the GB migration rate on the misorientation angles around the axis close to the low-index , and axes. It is shown that the GBs close to the special Σ3 , Σ19 , Σ9 , Σ11 , Σ5 , Σ13 and Σ17 misorientations (here Σ is the inverse density ofthe coincidence sites) exhibit a low DO rate. This is interpreted in terms of a decreased diffusivity in the special GBs. At the same time, GBs with a misorientation angle slightly below the value of 46.6° for the special Σ19 boundary exhibit the highest DO rate. A model is suggested which establishes a relationship between DO rate, diffusivity and mobility of the GB.