The synthesis of highly functionalized bis-β-lactams containing aromatic rings was achieved by thermal and microwave-assisted methods starting from easily available 2-(4-hydroxyphenyl)acetic acid and 2,2′-(propane-2,2-diyl)diphenol precursors. The approach to these valuable heterocyclic scaffolds involved formal [2π + 2π] cycloadditions between Schiff bases and novel bisketenes, which were generated in situ, followed by an electrocyclic reaction of zwitterionic intermediates. Reactions carried out under microwave irradiation were clean and gave high yields with significantly reduced reaction times. Interestingly, in the thermal method, the reaction proceeded in a stereospecific manner, and only the trans–cis or cis–cis isomers were formed. However, under the microwave conditions, the reaction proceeded stereoselectively, and other possible isomers such trans–trans and cis–trans isomers were formed in addition to the product formed under thermal conditions. More interestingly, when the two compounds that did not produce any products under thermal conditions were reacted under microwave conditions, one formed the trans–cis isomer and the other formed the cis–trans and trans–trans isomers as two products .