This work investigated the circular dichroic effect on the photoionization integral cross section of molecules in conjunction with irreducible tensor theory and effective operator formalism. The results show that the dichroic effect can be non-zero for complex orbitals, but becomes zero for all real orbitals due to time-reversal symmetry, within the electric dipole and Born-Oppenheimer approximations. Calculations were performed for carbon monoxide, boric acid, and fullerene, and implications of the first-order coefficient for the spin polarization of photoelectrons and the molecular axis orientation of photoions are discussed herein. The results of this work demonstrate that the photoionization of complex orbitals can cause photoions to become oriented such that photoions originating from complex conjugate orbitals are oriented opposite to one another. Due to electron-ion recoil, the spontaneous separation of these two kinds of photoions is expected for the point groups C n , , , C nh , and S n with n ≥ 3.