Unusual products were obtained from cycloadditions reactions of two series of styrylcyclohexene dienes with dienophiles maleic anhydride and N‐phenylmaleimide. Experimental studies revealed that various dienes 3 underwent an initial in‐situ dehydration/double bond rearrangement prior to cycloaddition with maleic anhydride to give products 5 in 78–88 % yields. Alternatively, the cycloadducts of the reactions of 4 with N‐phenylmaleimide were hydoxylated stereoselectively in the same pot to give products 7, along with the usual adducts 6 in 83–89 % yields. Further, the reactions of the diene 4 with the dienophile dimethyl acetylenedicarboxylate were also studied, leading to the formation of the respective adducts 10 in 72–81 % yields. The stereochemistry of the new products was assigned based on their spectroscopic data and, in some cases, with X‐ray crystallography experiments.