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The aim of this study was to provide data on the preliminary validation of a new clinician-report measure of mentalizing modalities, the Modes of Mentalization Scale (MMS), and to test its construct validity by using the MMS to investigate the relationship between mentalization and clinical variables, personality pathology, and attachment style. A random sample of 190 therapists rated an adult patient with no psychotic symptoms in the last 6 months using the MMS, the Clinical Questionnaire, a checklist of personality disorders (PDs), and the Adult Attachment Questionnaire. Exploratory factor analysis provided a 5-factor solution that accounted for 54% of the variance and represented 5 mentalizing modes: excessive certainty, concrete thinking, good mentalization, teleological thought, and intrusive pseudomentalization. Secure attachment style was positively predicted by good mentalization and negatively predicted by intrusive pseudomentalization; disorganized attachment style was positively predicted by concrete thinking; dismissing attachment style was predicted by concrete thinking; and preoccupied attachment style was predicted by teleological thought, good mentalization, and excessive certainty about mental states. Personality disorders had clinically and empirically relevant associations with MMS factors: good mentalization was negatively associated with schizoid PD, and intrusive pseudomentalization was negatively associated with avoidant PD and positively associated with histrionic and narcissistic PDs. The results did not seem to be influenced by therapists’ theoretical orientation. This study offers preliminary evidence for the validity and reliability of the MMS, which demonstrated promising psychometric properties. Further studies need to compare the MMS to a validated scale for the assessment of mentalization.