Organic light-emitting devices (OLEDs) containing self-assembled monolayers (SAMs) prepared by using p-substituted phenylphosponic acids on indium-tin-oxide electrodes were fabricated and examined to understand the substituent effect of the SAMs on the device performance. OLEDs modified by using (4-methoxyphenyl)phosphonic acid (MOPPA) SAMs or (4-chlorophenyl)phosphonic acid (CPPA) SAMs, both with electron withdrawing groups, had enhanced hole injection, reduced operating voltage, and remarkably increased current density and luminance efficiency compared with those without SAMs. The luminance efficiency which was the ratio of luminous flux to power for OLEDs containing CPPA SAMs and that for the OLEDs containing MOPPA SAMs were enhanced 2.2 and 1.9 times, respectively, in comparison with that of OLEDs without SAMs. CPPA SAMs significantly reduced the operating voltage of OLED by 24.8% compared with OLEDs without SAMs.