Two naphthalene diimides derivatives containing two different (alkyl and alkoxyphenyl) N-substituents were studied, namely, N,N′-bis(sec-butyl)-1,4,5,8-naphthalenetetracarboxylic acid diimide (NDI-s-Bu) and N,N′-bis(4-n-hexyloxyphenyl)-1,4,5,8-naphthalenetetracarboxylic acid diimide (NDI-4-n-OHePh). These compounds are known to exhibit electron transport due to their electron-deficient character evidenced by high electron affinity (EA) values, determined by electrochemical methods and a low-lying lowest unoccupied molecular orbital (LUMO) level, predicted by density functional theory (DFT) calculations. These parameters make the studied organic semiconductors stable in operating conditions and resistant to electron trapping, facilitating, in this manner, electron transport in thin solid layers. Current–voltage characteristics, obtained for the manufactured electron-only devices operating in the low voltage range, yielded mobilities of 4.3 × 10−4 cm2V−1s−1 and 4.6 × 10−6 cm2V−1s−1 for (NDI-s-Bu) and (NDI-4-n-OHePh), respectively. Their electron transport characteristics were described using the drift–diffusion model. The studied organic semiconductors can be considered as excellent candidates for the electron transporting layers in organic photovoltaic cells and light-emitting diodes