Psychiatric service dogs are an emerging complementary intervention for posttraumatic stress disorder (PTSD). Initial evidence suggests that partnership with a service dog may be related to less PTSD symptom severity. However, it remains unclear how or why this might occur. To address this gap, we conducted a longitudinal investigation of 82 post-9/11 military members or veterans and their PTSD service dogs to (1) evaluate service dog characteristics as potential predictors of efficacy, (2) assess dog and human characteristics as potential predictors of veteran-dog bond, and (3) explore potential mechanisms for mental health outcomes. Aim 1 results demonstrated that most service dog characteristics did not predict veterans' mental health outcomes, but lower service dog excitability was associated with less PTSD symptom severity at follow-up. Aim 2 results showed that closer dog-veteran relationships were associated with less excitable dog temperament. Aim 3 results indicated that worse mental health at follow-up was associated with greater use of the specifically trained PTSD service dog task to initiate a social greeting ("make a friend"), whereas better mental health was related to less use of dominance-based training methods, lower perceived emotional/logistical costs of service dog partnership, and closer veteran-dog relationships. More frequent use of the trained service dog task to signal when someone approaches from behind (cover/watch back) was associated with greater anxiety, but less PTSD symptom severity. Overall, veterans spent an average of 82% of their time with service dogs (assessed via Bluetooth proximity between dog collar and veteran smartphone), and most frequently asked their service dogs to perform the trained task for calming their anxiety (calm/comfort anxiety). The present study provides subjective and objective metrics of the heterogeneity among veteran-service dog dyads while also suggesting which of the assessed metrics might be potential mechanisms involved in the intervention.