An X-ray absorption spectroscopy study of the in-solution structures of the acetonitrile solvates of Ni2+, Co2+ and Ag+ cations has been performed. For the first two cations an octahedral arrangement of the acetonitrile molecules around the central metal atom has been found, while in the case of the Ag+ a tetrahedral arrangement has been found. In all cases the acetonitrile molecules were bonded to the central cation through, the nitrogen atom at distances R(Co2+-N) = 2.11 Angstrom, (Ni2+-N) 2.07 Angstrom, R(Ag+-N)= 2.27 Angstrom. The unusual high amplitude of the second peak in the radial distribution function, corresponding to the carbon atom of the cyanide group, for the three studied solvates, indicated that the angle formed by M-N-C was very close to 180 degrees. The quantitative analysis of the most intense multiple scattering contributions among those involving N atoms, C atoms from the cyanide group and C atoms form the methyl group provided values of Mn+-C-1 and Mn+-C-2 coordination distances as well as an estimate of coordination angles.