Heterojunction is an important structure for the development of photovoltaic solar cells. In contrast to homojunction structures, heterojunction solar cells have internal crystalline interfaces, which will reflect part of the incident light, and this has not been considered carefully before though many heterostructure solar cells have been commercialized. This paper discusses the internal reflection for various material systems used for the development of heterostructure-based solar cells. It has been found that the most common heterostructure solar cells have internal reflection less than 2%, while some potential heterojunction solar cells such as ITO/GaAs, ITO/InP, Si/Ge, polymer/semiconductors and oxide semiconductors may have internal reflection as high as 20%. Also it is worse to have a window layer with a lower refractive index than the absorption layer for solar cells. Ignoring this strong internal reflection will lead to severe deterioration and reduction of conversion efficiency; therefore measures have to be taken to minimize or prevent this internal reflection.