We investigate the manifestations of band structure engineering in few-layer PbI2-based heterostructures by probing their tunable optical properties. First, we have successfully prepared atomically thin flakes from PbI2 solution by two distinct approaches. A drop-casting of PbI2 solution onto various substrates followed by a simple heating process yields abundant flakes with different thickness and regular shape. Mechanical exfoliation of PbI2 bulk crystals, obtained from a low-temperature recrystallization process of PbI2 solution, also gives ultrathin PbI2 flakes of high quality. Moreover, these PbI2 flakes are employed to construct various van de Waals heterostructures. A significant enhancement of photoluminescence in MoSe2 interfaced with PbI2 was observed at different laser excitation intensity, due to the forming of type-I band alignment. Type-I band alignment can also be investigated in MoS2/PbI2 heterostructure, while type-II band alignment is built-in WSe2/PbI2 heterostructure. These results demonstrate that the strong interfacial coupling between PbI2 and other two-dimensional semiconductors can modulate their band alignment, and as a result, the exciton properties noticeably, which provides new insights of building a designer heterostructure device at the atomic level.