An Empirical Potential Structure Refinement of neutron and X-ray diffraction data combined with Extended Absorption Fine Structure evidence has been applied to the investigation of two distinct sets of complex aluminosilicate glasses containing different quantities of zinc. Data come from i) neutron and X-ray total scattering experiments, which have been performed at the ISIS neutron spallation source (SANDALS beamline) and at the European Synchrotron Radiation Facility (ID11 beamline), and from ii) EXAFS experiments which have been performed at the European Synchrotron Radiation Facility (BM23 beamline). By a careful examination of the modeled ensemble of atoms, a wide range of structural information has been extracted: coordination numbers, bond distances, cluster sizes, type of oxygen sharing and the preference of large cations to adopt a charge compensating role. The first series of glasses, which is characterized by a fixed network modifier element content (i.e. Na), shows how the introduction of Zn at the expense of Si and Al network forming elements does not significantly alter the polymerization degree, as a result of its dominant 4-fold coordination. In the case of the second series, which is characterized by fixed network forming element content (i.e. Si and Al), it is shown how the replacement of a network modifier element (i.e. Ca) with the introduction of Zn does not change the propensity of Zn to be mainly 4-fold coordinated, by promoting the network. Where appropriate the experimental results have been compared with classical theoretical approaches such as stoichiometric models based on Zachariasen's rules and computational routines.