Despite the unique properties of bismuth (Bi), there is a lack of two-dimensional (2D) heterostructures between Bi and other functional 2D materials. Here, a coherent strategy is reported to simultaneously synthesize rhombohedral phase Bi nanoflakes and bismuth oxychloride (BiOCl) nanosheets. The delicate balance between several reactions is mediated mainly for the reduction and chlorination in the chemical vapor transport (CVT) process. The Bi-BiOCl lateral heterostructures have been constructed via the coalescence of the two different 2D nanostructures. The characteristics of ambipolar conducting Bi and insulator-like BiOCl are elaborated by scanning microwave impedance microscopy (sMIM). This work demonstrates a way to construct a 2D Bi nanostructure in junction with its oxyhalide.