Schottky-type photodiodes’ quick responsiveness to light has attracted great attention worldwide. To increase their efficiency as electrodes or interlayers, a variety of materials have been employed. Two-dimensional materials such as MXene with an impressive ability to efficiently absorb light have been at the core of studies. On the other hand, the restacking challenge of 2-D materials poses important drawbacks limiting the benefit of their surface properties and large surface area. Preparation of 3-D materials using 2-D counterparts has been widely employed to alleviate the restacking problem. In this study, we synthesized 3-D V2C MXenes nanoflowers via a simple ultrasonic treatment followed by a freeze-drying process. The 3-D V2C MXenes nanoflowers were characterized by SEM, EDS, XRD, FT-IR, and XPS. The 3-D V2C MXenes nanoflowers were implemented as interlayers onto p-type and n-type Si wafers. The V2C MXenes/p-Si device has shown an excellent rectification ratio. The devices were measured under various illumination intensities. Electrical parameters were calculated via thermionic emission, Cheung, and Norde methods.