<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The cyanation of β‐ketophosphonates with TmsCN in the presence of organocatalyst CCT and p‐nitrophenol as additive affords α‐trimethylsilyloxy‐α‐cyanophosphonates, which under acidic hydrolysis are quantitatively converted into the desired alcohols.</p> </abstract>