The exploration and research of low-cost, environmentally friendly, and sustainable organic semiconductor materials are of immense significance in various fields, including electronics, optoelectronics, and energy conversion. Unfortunately, these semiconductors have almost poor charge transport properties, which range from ∼ 10−4 cm2⋅V−1⋅s−1 to ∼ 10−2 cm2⋅V−1⋅s−1. Vat orange 3, as one of these organic semiconductors, has great potential due to its highly conjugated structure. We obtain high-quality multilayered Vat orange 3 crystals with two-dimensional (2D) growth on h-BN surfaces with thickness of 10–100 nm using physical vapor transport. Raman’s results confirm the stability of the chemical structure of Vat orange 3 during growth. Furthermore, by leveraging the structural advantages of 2D materials, an organic field-effect transistor with a 2D vdW vertical heterostructure is further realized with h-BN encapsulation and multilayered graphene contact electrodes, resulting in an excellent transistor performance with On/Off ratio of 104 and high field-effect mobility of 0.14 cm2⋅V−1⋅s−1. Our results show the great potential of Vat orange 3 with 2D structures in future nano-electronic applications. Furthermore, we showcase an approach that integrates organic semiconductors with 2D materials, aiming to offer new insights into the study of organic semiconductors.