The kinetics of binary blends of poly(ethylene oxide)-block-poly(n-butyl methacrylate-random-propargyl methacrylate) (PEO-b-P(nBMA-r-PgMA)) diblock copolymer and Rhodamine B azide was investigated during a disorder-to-order transition induced by alkyne/azide click reaction. The change in the domain spacing and conversion of reactants as a function of annealing time were investigated by in situ small-angle X-ray scattering (SAXS) and infrared spectroscopy (IR), suggesting several kinetic processes with different time scales during thermal annealing. While a higher conversion can be realized by extending the annealing time, the microphase-separated morphology is independent of the annealing conditions, as long as both the reagents and final products have enough mobility.