The structure of prehnite Ca2Al(AlSi3O10)(OH)2, including H positions, has been determined by a combination of single-crystal X-ray diffraction and neutron powder diffraction on four natural samples. The symmetry of the average structure with Al/Si disordered at the T2 site is Pncm. However, for four of the crystals studied, numerous violations of the n- and c-glide reflection conditions indicate lower symmetry corresponding to space groups P2cm and P2/n and Al-Si ordered structures, possibly as domains of different symmetries and ordering within a single crystal. Time-of-flight neutron powder diffraction was carried out on a sample from Mali at 293 K and 2 K. The structure was refined in space group Pncm by Rietveld analysis. Although it was not possible to locate the missing H using the 293 K neutron data, these data were used to refine the H position located approximately by single-crystal XRD and to refine Uiso. For the 2 K neutron powder diffraction data, H was located directly by difference-Fourier synthesis and its refined position found to be in close agreement with that obtained by the combined XRD/neutron 293 K dataset.