We present ultrafast photoelectron spectroscopy of the charge-transfer-to-solvent reaction in a segregated TBAI (tetrabutylammonium iodide) molecular layer in aqueous solution. The reaction times and electron binding energies of transient species vary with TBAI concentration from a very low value of 1 X 10(-3) mol L-1, which is in contrast to NaI solution exhibiting no concentration (0.01-1.0 mol L-1) dependence. The result from soft X-ray N(1s) spectroscopy indicates that the photoelectron intensity in TBAI aqueous solution is about 70 times enhanced as compared to that in NH4Cl aqueous solution for an identical salt concentration, and TBA+ drags I- to the surface region. At high TBAI concentrations, electrons released from I- are trapped and held in the TBAI molecular layer owing to electrostatic attraction by TBA(+).