The gap states of tetratetracontane (C44H90; TTC), which is a model oligomer of polyethylene, was examined by using high-sensitivity UV photoemission spectroscopy (HS-UPS). The high sensitivity enabled us to directly observe the weak gap states distributed in the HOMO-LUMO gap from the valence band top to 3.0 eV below the vacuum level. On the basis of the density-of-states derived from UPS results, the tribocharging nature of polyethylene was discussed in comparison with our previous result for nylon-6,6 film.