This work addresses the chemical beam epitaxy (CBE) growth and interface properties of a new type of GaP(n)/GaAs(m)/InP(n)/GaAs(k) pseudomorphically strained superlattice structures. The structural properties of these highly strained heterostructures are discussed in light of high-resolution x-ray diffraction and transmission electron microscopy observations. In spite of the large lattice mismatch between the individual GaP, GaAs, and InP layers in the superlattice structures, it is demonstrated that due to a nearly perfect strain balance between GaP (in extension) and InP (in compression) layers, GaP/GaAs/InP/GaAs superlattices with thicknesses up to 1 mum can be achieved with CBE.