Temperature annealing is used as a tool to study the validity of network models for the nanostructure of hydrogenated amorphous silicon (a-Si:H) and its relation to defect states. The changes in the size of the dominant open volume deficiencies have been studied using Doppler broadening positron annihilation spectroscopy and Fourier transform infrared spectroscopy. It is shown that the dominant open volume deficiencies for as-deposited films are divacancies, which appear to agglomerate into larger open volume deficiencies up to 400 °C. Above this temperature, the largest open volume deficiencies are suggested to be released at the surface of the sample. Fourier transform photocurrent spectroscopy results indicate a dramatic increase in the density of various subgap defect state distributions during temperature annealing. In addition, at least four defect states have been identified. These findings cannot be directly explained by assuming solely dangling bonds as the dominant defects in a-Si:H. We discuss that a model based on an anisotropic disordered network with volume deficiencies does explain our findings better than the classical model based on a continuous random network with solely an isotropic distribution of coordination defects. The claim is made that next to dangling bonds not fully hydrogen-passivated vacancies are significantly contributing to the dominant defect states in a-Si:H.