GaAsPN semiconductors are promising material for the development of high-efficiency tandem solar cells on silicon substrates. GaAsPN diluted-nitride alloy is studied as the top-junction material due to its perfect lattice matching with the Si substrate and its ideal bandgap energy allowing a perfect current matching with the Si bottom cell. The GaP/Si interface is also studied in order to obtain defect-free GaP/Si pseudo-substrates suitable for the subsequent GaAsPN top junctions growth. Result shows that a double-step growth procedure suppresses most of the microtwins and a bi-stepped Si buffer can be grown, suitable to reduce the anti-phase domains density. We also review our recent progress in materials development of the GaAsPN alloy and our recent studies of all the different building blocks toward the development of a PIN solar cell. GaAsPN alloy with energy bandgap around 1.8 eV, lattice matched with the Si substrate, has been achieved. This alloy displays efficient photoluminescence at room temperature and good light absorption. An early-stage GaAsPN PIN solar cell prototype has been grown on a GaP(001) substrate. The external quantum efficiency and the I–V curve show that carriers have been extracted from the GaAsPN alloy absorber, with an open-circuit voltage above 1 eV, however a low short-circuit current density obtained suggests that GaAsPN structural properties need further optimization. Considering all the pathways for improvement, the 2.25% efficiency and IQE around 35% obtained under AM1.5G is however promising, therefore validating our approach for obtaining a lattice-matched dual-junction solar cell on silicon substrate.