In this work it is demonstrated how in situ high-resolution X-ray diffraction (HRXRD), performed during thermal annealing and employing a conventional laboratory source, can be used to obtain information on the evolution kinetics of very small complexes formed in an epitaxial layer. HRXRD allows the measurement of changes in the lattice parameter of the layer (i.e. the layer strain) with different annealing strategies (by linear temperature ramp or isothermal annealing). On the basis of these data and using an appropriate model, the dissolution energy values of the complexes can be extracted. The underlying idea is that every type of complex present in the layer gives a specific lattice strain which varies under annealing, allowing their evolution to be traced accurately. As an example, this methodology is applied to the study of N–H complexes formed in hydrogen-irradiated GaAs1−xNx/GaAs layers.