Irradiation of 5-styryl-1,3-dimethyluracil (5-SDU) with 2,3-dimethyl-2-butene (DMB) gives a [4+2] cycloadduct which is converted into a [2+2] cycloadduct on the prolonged irradiation. Triplet sensitization, quenching, and external heavy atom effect on the [4+2] photocycloaddition reaction demonstrate the singlet pathway and salt effect excludes a radical ion pair precursor possibility. Polar solvents increase the reaction efficiency implying a polar exciplex involvement in the [4+2] photocycloaddition reaction. Inverse temperature dependence both on the reaction and DMB fluorescence quenching of 5-SDU indicates the presence of a singlet exciplex intermediate.