Using multi-configuration Dirac-Fock method and the corresponding packages GRASP92 and RATIP, as well as the newly developed RERR06, we calculated inner- and outer-shell photoionization cross sections of configurations 1s2nl(n=2,3; l=s, p) of atomic lithium. In the calculations, the relaxation effect caused by photoionization of electrons was included. It was found that the relaxation effect plays an important role in the inner-shell photoionizational processes, contrary to the outer-shell photoionizational processes. Further, the effects of relaxation on inner-shell photoionizational processes from different states are not the same. It is more prominent for the excited states than the ground state, and for the higher excited states than the lower excited states.