AbstractWe develop and implement a Gaussian approach to calculate partial cross‐sections and asymmetry parameters for molecular photoionization. Optimal sets of complex Gaussian‐type orbitals (cGTOs) are first obtained by nonlinear optimization, to best fit sets of Coulomb or distorted continuum wave functions for relevant orbital quantum numbers. This allows us to represent the radial wavefunction for the outgoing electron with accurate cGTO expansions. Within a time‐independent partial wave approach, we show that all the necessary transition integrals become analytical, in both length and velocity gauges, thus facilitating the numerical evaluation of photoionization observables. Illustrative results, presented for NH₃ and H₂O within a one‐active‐electron monocentric model, validate numerically the proposed strategy based on a complex Gaussian representation of continuum states.