Photoluminescence has been used to investigate the behavior of Si‐implanted InP, submitted to a postimplantation rapid thermal annealing. Compared with the non‐implanted material, the implanted crystal displays a new broad band around 1.382 eV, in the low temperature (2 K) spectra. This band appears to be made of two unresolved recombination paths ascribed to the electron–acceptor (e,A°) and donor–acceptor pair recombinations of the silicon acceptor impurity substituted on phosphorus site. Besides the Zn‐related transitions tosandpexcited states, the selective excitation of the donor–acceptor pairs reveals additional recombination paths, ascribed to transitions to 2s3/2and 2p5/2(&Ggr;7and &Ggr;8) excited states of silicon. The acceptor behavior of Si in InP is hence given a definite support by this work. ©1995 American Institute of Physics.