Aluminum nitride was bonded with a titanium foil at 1400 °C for up to 1 h in Ar. The AlN/Ti interfacial reactions were investigated using analytical electron microscopy. Reaction layers, consisting of δ-TiN, τ2-Ti2AlN, γ-TiAl, α2-Ti3Al, a two-phase region (α2-Ti3Al + α-Ti), and α-Ti (Al, N) solid solution, were observed after annealing at 1400 °C for 0.1 h. Among these phases, the α2-Ti3Al and (α2-Ti3Al + α-Ti) were formed during cooling. Further diffusion of N atoms into the reaction zone precipitates a chopped fiber-like α2-Ti2AlN in the matrix of γ-TiAl, with [110]γ−TiAl//[11¯20]τ2−Ti2AlN and (1¯1¯1)γ−TiAl//(1¯10¯3)τ2−Ti2AlN, by substituting N atoms for one-half Al atoms after annealing at 1400 °C for 1 h. The released Al atoms, due to the precipitation of τ2-Ti2AlN, resulted in an ordered Al-rich γ-TiAl or Ti3Al5. Furthermore, the α-Ti (Al, N) was nitridized into a lamellar layer (δ-TiN + α-Ti) with [110]δ−TiN//[11¯20]α−Ti and (111)δ−TiN//(0001)α−Ti.