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The therapeutic alliance is a well-established predictor of psychotherapy outcome, and the ability to mentalize has been discussed as a change mechanism in psychotherapy. Low mentalization may lead to impairments in the alliance. In the present study, we assessed mentalization effects on the therapeutic alliance over the course of treatment. Thirty-seven patients diagnosed with depression or anxiety disorders received 25 ± 3 sessions of integrative cognitive behavioral therapy (outpatient setting). Patient's mentalization was coded by external raters based on transcripts of the first, eighth, 16th, and 24th therapy sessions, and the alliance quality was assessed from both patient and therapist perspectives after each session. The effects of mentalization on the alliance were investigated both within and between patients using hierarchical linear modeling. A higher patient ability to mentalize was related to a better therapist-reported but not patient-reported alliance during treatment. Mentalization did not show significant within-patient effects on the therapeutic alliance. To conclude, therapists may perceive a stronger therapeutic alliance with patients who exhibit a greater capacity for mentalization. It might be important for therapists to pay attention to a possible positive bias when patients present with a high ability to mentalize.