In this paper, the complete classification of solutions of defocusing complex modified KdV equation with a particular case of two-step initial condition is investigated by the finite-gap integration approach and Whitham modulation theory. The periodic wave solution and corresponding Whitham modulation equations for zero-phase, one-phase, two-phase are found. The self-similar wave structures in each case are composed of different building blocks: the plateau, vacuum, rarefaction wave, dispersive shock wave and two-genus region, which are studied in detail. The results of direct numerical simulations for the defocusing complex modified KdV equation agree well with those of Whitham modulation theory.