It is critically important to characterize the band alignment in semiconductor heterojunctions (HJs) because it controls the electronic and optical properties. However, the well‐known Anderson's model usually fails to predict the band alignment in bulk HJ systems due to the presence of charge transfer at the interfacial bonding. Atomically thin 2D transition metal dichalcogenide materials have attracted much attention recently since the ultrathin HJs and devices can be easily built and they are promising for future electronics. The vertical HJs based on 2D materials can be constructed via van der Waals stacking regardless of the lattice mismatch between two materials. Despite the defect‐free characteristics of the junction interface, experimental evidence is still lacking on whether the simple Anderson rule can predict the band alignment of HJs. Here, the validity of Anderson's model is verified for the 2D heterojunction systems and the success of Anderson's model is attributed to the absence of dangling bonds (i.e., interface dipoles) at the van der Waal interface. The results from the work set a foundation allowing the use of powerful Anderson's rule to determine the band alignments of 2D HJs, which is beneficial to future electronic, photonic, and optoelectronic devices. The band alignment of stacked 2D material heterojunctions is experimentally proven to follow the Anderson's model. Based on this discovery it is demonstrated that electron affinity and band gap values are sufficient to construct the band alignment of stacked 2D heterojunctions.