[en] Highlights: • XPS is used to probe the electronic environment of cations and anions. • The impact of the anion on the electronic environment of the cation is revealed. • With the increasing of the weighting of Cl⁻, the N 1s binding energy is decreased. • The electronic environment of the anion-based component is also compared. • Sn 3d and Cl 2p binding energies decrease with the increasing of the weighting of Cl⁻. X-ray photoelectron spectroscopy is used to probe the electronic environment of cations and anions for three binary and one ternary chlorostannate ionic liquid mixtures. The impact of the weighting of Cl⁻ on the electronic environment of the cation-based nitrogen atom is revealed in detail. With the increasing of the concentration of Cl⁻, the N 1s binding energy is decreased. The electronic environment of the anion-based component is also compared based upon Sn 3d_5/2 and Cl 2p_3/2 binding energies. It is found that with the increasing of the weighting of Cl⁻, binding energies of Sn 3d_5/2 and Cl 2p_3/2 both decrease.