The influence of metal-organic frameworks (MOFs) as additives is herein described for the reaction of n-alkyl aldehydes in the presence of methylvinylketone and triphenylphosphine. In the absence of a MOF, the expected Morita-Baylis-Hillman product, a β-hydroxy enone, is observed. In the presence of MOFs with UMCM-1 and MOF-5 topologies, the reaction is selective to Aldol-Tishchenko products, the 1 and 3 n-alkylesters of 2-alkyl-1,3-diols, which is unprecedented in organocatalysis. The (3-oxo-2-butenyl)triphenylphosphonium zwitterion, a commonly known nucleophile, is identified as the catalytic active species. This zwitterion favors nucleophilic character in solution, whereas once confined within the framework, it becomes an electrophile yielding Aldol-Tishchenko selectivity. Computational investigations reveal a structural change in the phosphonium moiety induced by the steric confinement of the framework that makes it accessible and an electrophile.