The applicability of atom probe to the characterization of photovoltaic devices is presented with special emphasis on high efficiency III–V and low cost ITO/a-Si:H heterojunction cells. Laser pulsed atom probe is shown to enable subnanometer chemical and structural depth profiling of interfaces in III–V heterojunction cells. Hydrogen, oxygen, and phosphorus chemical profiling in 5-nm-thick a-Si heterojunction cells is also illustrated, along with compositional analysis of the ITO/a-Si interface. Detection limits of atom probe tomography useful to semiconductor devices are also discussed. Gaining information about interfacial abruptness, roughness, and dopant profiles will allow for the determination of semiconductor conductivity, junction depletion widths, and ultimately photocurrent collection efficiencies and fill factors.