Signatures of molecular structures immediately after the ultrafast crossing through a conical intersection (CI) were found in 1,2,3,4,5-pentamethyl- cyclopentadiene (PMCPD) and 1,3-cyclohexadiene (CHD). The molecules were excited at 267 nm, and the structures immediately after reaching their ground electronic states were observed using a structure-sensitive photoionization/ photoelectron technique. PMCPD is found to revert to its original structure, but CHD is immediately launched toward the ring-opened structure upon crossing through the CI, proving that the ring opening reaction mechanism proceeds completely within an ultrafast time scale. The resulting hexatriene is observed to have a poorly defined fluxional structure. (C) 2009 Elsevier B. V. All rights reserved.