The structures of hydrated guanidinium, Gdm(+)(H2O)(n), where n = 1-5, were investigated with infrared photodissociation spectroscopy and with theory. The spectral bands in the free O-H (similar to 3600-3800 cm(-1)) and free N-H (similar to 3500-3600 cm(-1)) regions indicate that, for n between 1 and 3, water molecules bind between the NH2 groups in the plane of the ion forming one hydrogen bond with each amino group. This hydration structure differs from Gdm(+) in solution, where molecular dynamics simulations suggest that water molecules form linear H-bonds with the amino groups, likely a result of additional water-water interactions in solution that compete with the water-guanidinium interactions. At n = 4, changes in the free O-H and bonded O-H (similar to 3000-3500 cm(-1)) regions indicate water-water H-bonding and thus the onset of a second hydration shell. An inner shell coordination number of n = 3 is remarkably small for a monovalent cation. For Gdm(+)t(H2O)(5), the additional water molecule forms hydrogen bonds to other water molecules and not to the ion. These results indicate that Gdm(+) is weakly hydrated, and interactions with water molecules occur in the plane of the ion. This study offers the first experimental assignment of structures for small hydrates of Gdm(+), which provide insights into the unusual physicochemical properties of this ion.