Si(001) single crystal was implanted with hydrogen ions with energy 135 keV and dose 5 × 1016 cm–2. After implantation, Si:H samples were annealed at 450 and 650 °C under atmospheric and enhanced hydrostatic pressure (1.1 GPa). Defect structure of as‐implanted and processed Si:H was determined by X‐ray scattering methods. Two types of defect clusters contributing to diffuse scattering were revealed: (i) the defects produced by hydrogen diffusion, characterized by small dimensions, with concentration dependent on annealing temperature; (ii) rather large bubbles and platelets produced due to hydrogen agglomeration at defects with negative dilatation. The samples annealed under high pressure contain large defects with the double force tensor equivalent to the dislocation loops one. It is found that the high pressure heat treatment retards the hydrogen diffusion. Distribution of diffuse scattering around the 004 reciprocal lattice point for each type of defects is simulated and compared with the experimental data. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)