In cyanine dye, photoisomerization paths involving multiphoton processes were found by two-color two-pulse correlation of ultrafast transient absorption spectroscopy. The reaction efficiency depended on the interval between two pump pulses, UV and NIR pulses, as well as the fluence of the NIR pulse, but was little dependent on that of the UV pulse. These results indicate that the new photoisomerization paths involve the NIR multiphoton process and/or the UV one-photon process. The difference in two-pulse correlation between positive and negative time regions revealed a new reaction path that had the highest branching ratio of cis isomer to other leuco forms. (C) 2011 Elsevier B.V. All rights reserved.