Electronic transitions of protonated benzene ((A) over tilde B-1(2)<-(X) over tilde (1)A(1), origin at 325 nm) and alpha-protonated fulvene ((A) over tilde (1)A'<-(X) over tilde (1)A', at 335 nm) trapped in 6 K neon matrices have been detected. The cations were produced from several different precursors, mass-selected, and co-deposited with neon. After neutralization of the cations, the electronic transitions of cyclohexadienyl (onsets at 549 and 310 nm) and alpha-hydrogenated fulvene (532 and 326 nm) radicals were identified. Upon excitation of cyclohexadienyl to the (B) over tilde B-2(1) state, photoisomerization to an open-chain structure and alpha-hydrogenated fulvene was observed.