Electron trapping in naphthalene is studied by analysis of the space-charge-limited and thermally stimulated currents as a function of applied voltage and temperature. The two methods are used on naphthalene single crystals, with continuous electron injection from a silver contact. The use of the two techniques allows a quantitative determination of the characteristics of deep and shallow traps. Three monomolecular current peaks were observed. Activation energies of 0.5, 0.79, and 1.1 eV, and cross sections of 8.8 × 10−20, 6.9 × 10−16, and 1.0 × 10−18 cm2, were calculated for the corresponding discrete trapping levels of the charge carriers. The behavior observed for space-charge-limited current was a current-voltage characteristic of a single set of traps, with an activation energy of 0.71 eV, and a cross section of 7.1 × 10−16 cm2. The results showed that the use of only space-charge-limited current is not good enough for a characterization of the traps of the material.