We investigate the phase structure of strongly interacting matter and baryon number fluctuations in the Polyakov loop improved Nambu--Jona-Lasinio (PNJL) model. The calculation shows that both the chiral and deconfinement transitions, as well as their coincidence and separation determine the basic QCD phase structure. The contour maps and the three-dimensional diagrams of the net-baryon kurtosis and skewness present well the trace of QCD phase structure. Comparing with the experimental data, we find that the existence of a critical end point (CEP) of chiral transition is crucial to explain the non-monotonic energy dependence and the large deviation from Poisson baseline of net-proton kurtosis. In particular, the relation between the chiral and deconfinement transitions in the crossover region is also reflected by the baryon number fluctuations. This study shows that the measurements of higher moments of multiplicity distributions of conserved charges are powerful to investigate the criticality and even the chiral and deconfinement transitions in the crossover region.