Recently it was reported that cycloaddition of 6,6-disubstituted cyclohexa-2,4-dienone, 1 with cyclopentadiene gave solely the adduct of type 1.while its reaction with 1,3-cyclohexadiene gave both Ⅱ and Ⅲ. Semiempirical MO calculations were done to elucidate the origin of the selectivity difference between the two dienes. Cycloaddition of 1 with cyclopentadiene is controlled thermodynamically to give only 1-diene adduct by ΔGvalues of 10.6-20.3 kcal/mol, while its reaction with 1,3-cyclohexadiene does not show 1-diene/1-dienophile selectivity due to similar stabilities of the two adducts. Thermodynamic parameters also show that 두애 adducts are more fabourably fromed in the cycloadditions of 1 with both cyclopentadiene and 1,3-cyclohexadiene, which coincides with experimental observations. Cope rearrangements of endo adducts are another avenue to convert between 1-diene and 1-dienophile.