Abstract Photolysis (λ= 254 nm) of 4-(t-Bu)-substituted [b]-fused bi-and tricyclic pyrandiones 5 affords title compounds 4 in good yields as well as small amounts of spiroalkanediones 8. The alkyl-substitution pattern at C (4) of the pyran ring in 5 determines the relative amount of α vs. β-cleavage products obtained from the primarily formed acyl-vinyloxy biradical.