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]. Visible plasma emission near the He-I 587.6-nm and Ar-II 476.5-514.5-nm lines are simultaneously recorded by splitting a single visible image of the shock into two different fast-framing cameras with different narrow bandpass filters (589 ± 5 nm for observing the He-I line and 500 ± 25 nm for the Ar-II lines). For conditions in these experiments (pre-shock ion and electron densities ≈ 5 × 10 14 cm −3 , ion and electron temperatures of ≈ 2.2 eV, and relative plasma-merging speed of 22 km/s), the observationally inferred magnitude of He/Ar shock-front separation and the shock widths themselves are < 1 cm, which correspond to ∼ 50 post-shock thermal ion-ion mean free paths. The experiments are in reasonable qualitative and quantitative agreement with results from 1D multi-fluid simulations using the chicago code. Moreover, the experiment and simulation results are consistent with first-principles theoretical predictions that the lighter He ions diffuse farther ahead within the overall shock front than the heavier Ar ions.