This study investigated the growth of AlN epitaxial films on 2-in. Si(111) via metal-organic chemical vapor deposition. By introducing triethylboron (TEB) during trimethylaluminum pretreatment, a nearly crack free AlN epilayer with a thickness of 500 nm was acquired. The x-ray diffraction rocking curves of AlN (002) and (102) exhibited full width at half maximum values of 0.22° and 0.36°, respectively. Atomic force microscopy image analysis showed that after the introduction of TEB, larger grains appeared on the surface of Si(111) substrate, promoting the 3D growth pattern of the subsequent AlN buffer layer. Laytec reflection curves depicted the morphological transition from 3D to 2D growth mode during AlN deposition. At the same time, the curvature value was significantly reduced by 20 km−1, and the Raman spectrum peak of E2(high) shifted from 648.7 to 652.5 cm−1, indicating that the surface tensile stress was greatly reduced, effectively suppressing the crack problem of AlN on Si(111).