The structural properties of highly mismatched III-V semiconductors with small amounts of Bi are still not well understood at the atomic level. In this chapter, the potential of cross-sectional scanning tunneling microscopy (X-STM) to address these questions is reviewed. Special attention is paid to the X-STM contrast of isovalent impurities in the III-V system, which is discussed on the basis of theoretical STM images of the (110) surface using density functional theory (DFT) calculations. By comparing high-resolution X-STM images with complementary DFT calculations, Bi atoms down to the third monolayer below the InP (110) surface are identified. With this information, the Short-range ordering of Bi is studied, which reveals a strong tendency toward Bi pairing and clustering. In addition, the occurrence of Bi surface segregation at the interfaces of an InP/InP1−xBix/InP quantum well with a Bi concentration of 2.4 % is discussed.