The reaction sequence and microstructure evolution of a crystalline MgB2 layer were examined during ex situ annealing of evaporated amorphous boron (a-B) with Mg vapor. Mg was found to migrate rapidly into the a-B layer in the initial stage of reaction with a uniform concentration of about 12 at.%. A thin layer of crystalline MgO was observed at the interface between a-B and the Al2O3 substrate. It was identified that an MgB2 layer started to form at the surface by the nucleation and growth process in polycrystalline form. It appears that there exists two distinct growth fronts in the MgB2 layer: one lying at the surface and the other lying at the interface between the MgB2 layer and the a-B. The microstructural evolution of this layer showed significant differences depending on the location of these two growth fronts.