We discuss the thermal phase structure of quantum chromodynamics (QCD) at zero real chemical potential (μR=0) from the viewpoint of canonical sectors. The canonical sectors take the system to pieces of each elementary excitation mode and thus seem to be useful in the investigation of the confinement–deconfinement nature of QCD. Since the canonical sectors themselves are difficult to compute, we propose a convenient quantity which may determine the structural changes of the canonical sectors. We discuss the quantity qualitatively by adopting lattice QCD prediction for the phase structure with finite imaginary chemical potential. In addition, we numerically estimate this quantity by using the simple QCD effective model. It is shown that there should be a sharp change of the canonical sectors near the Roberge–Weiss endpoint temperature at μR=0. Then, the behavior of the quark number density at finite imaginary chemical potential plays a crucial role in clarifying the thermal QCD properties.