Purpose: This study aimed to assess the accuracy of MRI in identifying ulnar collateral ligament (UCL), radial collateral ligament (RCL), and volar plate (VP) injuries of the metacarpophalangeal joint (MCPJ) of the thumb by comparing with diagnostic arthroscopy. Methods: A total of 56 consecutive patients (56 thumbs) who underwent arthroscopy of MCPJ of thumb were enrolled. MRI findings reviewed by consensus reading of two blinded radiologists were compared with arthroscopic examination. Statistical data, including sensitivity, specificity, accuracy, were analyzed. Additionally, the performance characteristics between 3.0-tesla (39 thumbs) and 1.5-tesla (17 thumbs) MRI and acute (≤4 weeks after injury) and chronic (>4 weeks) injuries were compared. Results: Of the 56 thumbs, 38 thumbs (67.9%) showed complete correspondence between MRI and arthroscopic findings. The sensitivity, specificity and accuracy of MRI for detecting UCL injuries were 78.8%, 87.0%, and 82.1%, respectively. The sensitivity, specificity and accuracy of MRI for detecting RCL injuries were 85.7%, 91.4%, and 85.7%, respectively. The sensitivity, specificity, and accuracy of MRI for detecting VP injuries were 89.5%, 89.2%, and 81.0%, respectively. 3.0-tesla MRI showed higher correspondence with arthroscopic observation (76.9%) than 1.5-tesla MRI (47.1%) (p = 0.028). For acute injuries, 78.4% showed complete correspondence between MRI and arthroscopic findings, whereas 47.4% with chronic injuries revealed complete agreement (p = 0.019). Conclusion: Overall, MRI is moderately effective in evaluating ligamentous lesions around MCPJ of thumb, but MRI is more sensitive in diagnosing acute injuries. Furthermore, 3.0-tesla MRI can provide results with better accuracy for diagnosing ligamentous lesions around MCPJ of thumb. However, the sensitivity and the specificity are not applicable to all ligament injuries, but only the severe one which would agree for surgical options.