The emission of spectator neutrons and protons in ultracentral collisions of Bi with the same (Bi) or lighter (W, Cu) target nuclei has been simulated using the Abrasion-Ablation Monte Carlo for Colliders model with MST clustering (AAMCC-MST). It was shown that the detection of forward neutrons and protons in such collisions allows the analysis of the n∕p ratio at the nuclear periphery. The cross-sections to produce a given number of spectator neutrons Nn, the average number of spectator neutrons ⟨Nn⟩ and protons ⟨Np⟩ in ultracentral collisions were calculated with and without consideration of the neutron skin in Bi. The ratio ⟨Nn∕Np⟩ was found to be particularly sensitive to the presence of neutron skin in Bi–W collisions, providing a potential probe of the enrichment of the nuclear surface by neutrons. However, this sensitivity disappears in Bi–Cu collisions due to the involvement of inner nuclear layers to the spectator emission.