Angiomatous meningiomas comprise numerous blood vessels. The ability to clearly diagnose angiomatous meningiomas preoperatively or intraoperatively is crucial for developing surgical plans and prognosis. In this study, we combined the second harmonic, two-photon excited fluorescence, and spectroscopic techniques to realize a label-free study of angiomatous meningiomas. Results show that this multiphoton technique can identify the endogenous components of angiomatous meningioma and visualize its microstructure. Furthermore, combined with image analysis techniques, the multiphoton technique can further automatically locate vessels and calculate number of vessels. With the rapid development in fiber optic and multiphoton endoscopic technologies, multiphoton technique poses as a new technique for the clinical diagnosis of angiomatous meningiomas.