Single-wall carbon nanotubes (SWCNTs) exhibit resonant absorption localized in specific spectral regions. To expand the light spectrum that can be utilized by SWCNTs, we have encapsulated squarylium dye into SWCNTs and clarified its microscopic structure and photosensitizing function. X-ray diffraction and polarization-resolved optical absorption measurements revealed that the encapsulated dye molecules are located at an off center position inside the tubes and aligned to the nanotube axis. Efficient energy transfer from the encapsulated dye to SWCNTs was clearly observed in the photoluminescence spectra. Enhancement of transient absorption saturation in the S1 state of the semiconducting SWCNTs was detected after the photoexcitation of the encapsulated dye, which indicates that ultrafast (< 190 fs) energy transfer occurred from the dye to the SWCNTs.