The study of the structure and dynamics of network-forming materials is reviewed. Experimental techniques used to extract key structural information are briefly considered. Strategies for building simulation models, based on both targeting key (experimentally-accessible) materials and on systematically controlling key model parameters, are discussed. As an example of the first class of materials, a key target system, SiO2, is used to highlight how the changing structure with applied pressure can be effectively modelled (in three dimensions) and used to link to both experimental results and simple structural models. As an example of the second class the topology of networks of tetrahedra in the MX2 stoichiometry are controlled using a single model parameter linked to the M-X-M bond angles. The evolution of ordering on multiple length-scales is observed as are the links between the static structure and key dynamical properties. The isomorphous relationship between the structures of amorphous Si and SiO2 is discussed as are the similarities and differences in the phase diagrams, the latter linked to potential polyamorphic and 'anomalous' (e.g. density maxima) behaviour. Links to both two-dimensional structures for C, Si and Ge and near-two-dimensional bilayers of SiO2 are discussed. Emerging low-dimensional structures in low temperature molten carbonates are also uncovered.