Zirconium carbide (ZrC) components were induced as coating modification on carbon/carbon (C/C). These ZrC–C/C specimens were investigated after atomic oxygen (AO) exposure for different assessment times, low earth orbit (LEO) ground-based environmental simulator was employed. The results indicate that ZrO2 is the major production generated by the AO chemical reaction with the ZrC coating. Upon further exposure to AO, the production of ZrO2 would drop off, then exfoliate easily, due to the mechanical impacting effect. Then the exposed graphite matrix and carbon fiber get corroded. Amorphous diamond-like carbon (DLC) is detected by X-ray photoelectron spectroscopy during AO exposure. Bending strength performance increased by 25% under AO exposure at first 10 h, then dropped by 52.1% from 10 h to 30 h of AO exposure. The AO damage mechanisms of ZrC–C/C composites are revealed.