BACKGROUND: Debate exists over the extent to which dysfunctions arising from mild traumatic brain injury (mTBI) are distinct from posttraumatic stress disorder (PTSD). METHODS: This study investigated 1) the white matter integrity of participants with either mTBI or PTSD, and 2) the relationship between white matter integrity and postconcussive syndrome. The sample comprised 110 civilians (mTBI group = 40; PTSD group = 32; age- and sex-matched trauma-exposed control subjects = 38) recruited from community advertising. Indicators of white matter abnormalities were fractional anisotropy, mean diffusivity, axial diffusivity, and radial diffusivity. PTSD symptoms were indexed by the Clinician-Administered PTSD Scale, and postconcussive symptoms were assessed using the Somatic and Psychological Health Report measure. RESULTS: Fractional anisotropy was reduced in mTBI participants in the corpus callosum, tracts of the brainstem, projection fibers, association fibers, and limbic fibers compared with both PTSD and trauma-exposed control subjects. This decrease in fractional anisotropy was observed in the context of concurrent changes in radial diffusivity, axial diffusivity, and mean diffusivity. Postconcussive symptoms were largely explained by PTSD severity rather than by changes in brain white matter. mTBI appears to be characterized by distinct reductions in white matter integrity, and this cannot be attributed to PTSD. CONCLUSIONS: PTSD symptoms appear to be more strongly associated with postconcussive syndrome than with white matter compromise. These findings extend epidemiological evidence of the relative associations of PTSD and mTBI with postconcussive syndrome.