To investigate the finite-volume effects on the chiral symmetry restoration and the deconfinement transition for a quantum chromodynamics (QCD) system with Nf=2Nf=2 (two quark flavors), we apply the Polyakov-loop extended Nambu–Jona-Lasinio model by introducing a chiral chemical potential μ5 artificially. The final numerical results indicate that the introduced chiral chemical potential does not change the critical exponents, but shifts the location of critical end point (CEP) significantly; the ratios for the chiral chemical potentials and temperatures at CEP, μc/μ5c and Tc/T5c, are significantly affected by the system size R. The behavior is that Tc increases slowly with μ5 when R is “large” and Tc decreases first and then increases with μ5 when R is “small.” It is also found that for a fixed μ5, there is a Rmin, where the critical end point vanishes and the whole phase diagram becomes a crossover when R<Rmin. Therefore, we suggest that for the heavy-ion collision experiments, which is to study the possible location of CEP, the finite-volume behavior should be taken into account.