Abstract Various studies have been dedicated to quantifying the atmospheric chemical effects of energetic electron precipitation (EEP), but the contribution from relativistic electron precipitation (REP) was largely overlooked. Based on the precipitating fluxes estimated from Polar‐orbiting Observational Environmental Satellites, we quantify the REP‐induced atmospheric chemical effects using the Whole Atmosphere Community Climate Model. Present results show that direct stratospheric ionization caused by REP can enhance the NOx concentration by a factor of ∼2.58 at ∼37 km altitude, and the HOx concentration by a factor of ∼6.41 at ∼44 km altitude. As for the annual variation, REP causes an additional ozone loss of ∼16.2%–17.1% at ∼30–35 km altitude during winter. Moreover, REP’s impact is not confined to winter since the resultant NOx and HOx production occurs in situ. Therefore, neglecting REP would significantly underestimate EEP’s total effects on the stratospheric ozone.