The applicability of vinyl nitriles in the preparation of pharmaceuticals, polymers, and other valuable materials benefits from robust preparative methodologies. In this work, we present a novel approach for the synthesis of vinyl nitriles based on the Ramberg–Bäcklund olefination reaction (RBR). While there are few examples for accessing functionalized olefins using the RBR, we believe that this methodology embodies useful means for installing privileged vinylnitrile building blocks, such as the acrylonitrile fragment of the US FDA-approved antiviral rilpivirine.