An intramolecular [4+2] cycloaddition of 1-(9-anthrylchlorophosphino)-1,4-diphenylbut-1-en-3-yne produced the 1-(chlorophosphino)-1,4-diphenyl-1,3-butadiene derivative incorporated with a dibenzobarrelene skeleton, the following reactions of which gave the corresponding secondary phosphine oxide and phenylphosphine sulfide. The secondary phosphine oxide was deprotonated with butyllithium followed by treatment with methyl iodide to give methylphosphine oxide. The phenylphosphine sulfide was desulfurized with P(NMe2)3 to give the corresponding phenylphosphine, which was converted to the oxide and selenide and AuCl and BH3 complexes. Their structures were determined by X-ray crystallography. These compounds show blue fluorescence in solution (ΦF = 0.49–0.86) and the solid state (ΦF = 0.02–0.72) in a narrow range (λem = 442–463 nm) except the phenylphosphine selenide with a low fluorescence efficiency. Their photophysical properties were considered theoretically. The secondary phosphine oxide and the methylphosphine oxide were optically resolved by means of HPLC equipped with a chiral column, and the chiroptical properties were investigated to show weak circular polarized luminescence (CPL) of |gem| = 2.8–8.8 × 10−4.