The report discussed recent experimental data on reaction kinetics in the presence of cationic chalcogenorganics and halogenorganic compounds, as well as xenon derivatives, which shed light on observed catalytic effects. Special attention was given to the design of tandem catalytic systems involving σ-hole carriers and unusual catalytic pathways mediated by these compounds. Additionally, this presentation addressed the stability and reactivity of the employed organocatalysts, along with the influence of competitive substrate coordination onto sigma-holes.