The Diels-Alder reaction of β-fluoro-β-nitrostyrenes with cyclic 1,3-dienes was investigated. A series of novel monofluorinated norbornenes was prepared in up to 97% yield. The reaction with 1,3‑cyclohexadiene permits the preparation of monofluorinated bicyclo[2.2.2]oct-2-enes. The kinetic data of the reaction with cyclopentadiene and cyclohexadiene-1,3 were used to calculate activation parameters. Furthermore, the synthetic utility of the cycloadducts obtained was demonstrated.