Recent advances in magnetic resonance imaging (MRI) are allowing neuroscientists to gain critical insights into the neural networks mediating a variety of cognitive processes. This work investigates structural and functional connectivity in the human brain under different experimental conditions through multimodal MRI acquisitions. To define the nodes of a full-brain network, a set of regions was identified from resting-state functional MRI (fMRI) data using spatial independent component analysis (sICA) and a hierarchical clustering technique. Diffusion-weighted imaging (DWI) data were acquired from the same subjects and a probabilistic fiber tracking method was used to estimate the structure of this network. Using features originating from graph theory, such as small-world properties and network efficiency, we characterized the structural and functional connectivities of the full-brain network and we compared them quantitatively. We showed that structural and functional networks shared some properties in terms of topology as measured by the distribution of the node degrees, hence supporting the existence of an underlying anatomical substrate for functional networks.