We apply high-level ab initio methods to describe the electronic structure of small clusters of ammonia and dimethyl ether (DME) doped with sodium, which provide a model for solvated electrons. We investigate the effect of the solvent and cluster size on the electronic states. We consider both energies and properties, with a focus on the shape of the electronic wave function and the related experimental observables such as photoelectron angular distributions. The central quantity in modeling photoionization experiments is the Dyson orbital, which describes the difference between the initial N-electron and final (N-1)-electron states of a system. Dyson orbitals enter the expression of the photoelectron matrix element, which determines total and partial photoionization cross sections. We compute Dyson orbitals for the Na(NH3)(n) and Na(DME)(m), clusters using correlated wave functions (obtained with equation-of-motion coupled-cluster model for electron attachment with single and double substitutions) and compare them with more approximate Hartree-Fock and Kohn-Sham orbitals. We also analyze the effect of correlation and basis sets on the shapes of Dyson orbitals and the experimental observables.