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The precise effect of oxide understoichiometry on bulk oxide catalytic properties continues to remain a subject of intense investigation. Of specific interest in this regard is the role of oxygen vacancies present on bulk ceria catalysts that have recently been reported to represent a more cost‐effective alternative to the more toxic and expensive catalysts used industrially for the selective hydrogenation of acetylene to ethylene. Contrasting claims as to the effect of surface reduction on hydrogenation rates exist in the open literature, with vacancy formation attributed, in separate studies, either a favorable or a deleterious role in effecting hydrogenation turnovers. We report here the non‐monotonic behavior of ethene hydrogenation rates that subsumes both of these trends as a function of degree of surface reduction over a sufficiently large range of pre‐reduction temperatures. Steady state transient kinetic and isotopic exchange data combined with in‐situ titration experiments suggest that this non‐monotonic trend can be attributed not to a change in either the kinetic relevance of specific elementary steps or the hydrogenation mechanism, but rather to site requirements that stipulate the need for two distinct, proximal sites. We also show that the sensitivity of hydrogenation rates to surface reduction can be altered by varying ceria surface termination, with the more open (110) and (100) surfaces exhibiting a less asymmetric effect of surface reduction on ethene hydrogenation rates.