We observe shock-front separation and species-dependent shock widths in multi-ion-species collisional plasma shocks, which are produced by obliquely merging plasma jets of a He/Ar mixture (97% He and 3% Ar by initial number density) on the plasma liner experiment [S. C. Hsu et al., IEEE Trans. Plasma Sci. 46, 1951 (2018)]. Visible plasma emission near the He-I 587.6-nm and Ar-II 476.5-514.5-nm lines is simultaneously recorded by splitting a single visible image of the shock into two different fast-framing cameras with different narrow bandpass filters (589 +/- 5nm for observing the He-I line and 500 +/- 25nm for the Ar-II lines). For conditions in these experiments (pre-shock ion and electron densities approximate to 5x1014 cm(-3), ion and electron temperatures of approximate to 2.2 eV, and relative plasma-merging speed of 22km/s), the observationally inferred magnitude of He/Ar shock-front separation and the shock widths themselves are<1cm, which correspond to similar to 50 post-shock thermal ion-ion mean free paths. These experimental length scales are in reasonable qualitative and quantitative agreement with results from 1D multi-fluid simulations using the chicago code. However, there are differences between the experimentally inferred and simulation-predicted ionization states and line emission intensities, particularly in the post-shock region. Overall, the experimental and simulation results are consistent with theoretical predictions that the lighter He ions diffuse farther ahead within the overall shock front than the heavier Ar ions. Published under license by AIP Publishing.