Exploring emerging two-dimensional (2D) van der Waals (vdW) semiconducting materials and precisely tuning their electronic properties at the atomic level have long been recognized as crucial issues for developing their high-end electronic and optoelectronic applications. As a III-VI semiconductor, ultrathin layered hexagonal GaTe (h-GaTe) remains unexplored in terms of its intrinsic electronic properties and band engineering strategies. Herein, we report the successful synthesis of ultrathin h-GaTe layers on a selected graphene/SiC(0001) substrate, via molecular beam epitaxy (MBE). The widely tunable quasiparticle band gaps (∼2.60-1.55 eV), as well as the vdW quantum well states (QWSs) that can be strictly counted by the layer numbers, are well characterized by onsite scanning tunneling microscopy/spectroscopy (STM/STS), and their origins are clearly addressed by density functional theory (DFT) calculations. More intriguingly, distinctive 8|8E and 4|4P (Ga) mirror twin boundaries (MTBs) are identified in the ultrathin h-GaTe flakes, which can induce decreased band gaps and prominent p-doping effects. This work should deepen our understanding on the electronic tunability of 2D III-VI semiconductors by thickness control and line defect engineering, which may hold promise for fabricating atomic-scale vertical and lateral homojunctions toward ultrascaled electronics and optoelectronics.