Chromone-3-ylmethyl aryl ethers with unsubstituted ortho-positions have been found to undergo a novel domino [1,3]-[1,3]-rearrangement to give 4'-hydroxyhomoisoflavones under thermal conditions while the para-substituted ethers lead to 2'-hydroxyhomoisoflavones involving an O- to C-[1,3]-migration, instead of the expected Claisen rearrangement. A few cis-homopterocarpans have been synthesized using the 2'-hydroxyhomoisoflavones obtained from the thermal [1,3]-rearrangement of chromene-3-ylmethyl aryl ethers.