Bioglass 45S5, the prototype of bioactive melt-quenched silicate glasses, was modeled by means of Car-Parrinello molecular dynamics (CPMD) simulations. Although long-range structural properties cannot be modeled by using this ab initio approach, the accuracy of CPMD simulations is exploited here to provide insight into the short-range structure and to analyze vibrational and electronic properties of this biomaterial. Detailed structural analysis in the short-range scale provided insight into the local environment of modifier Na and Ca ions: a possible key role of these cations in organizing the glass network by connecting different chains and fragments into specific, rather flexible geometries was proposed. The individual contributions of different species to the vibrational density of states were separated and discussed, allowing the identification of specific features in the vibrational spectrum, such as those related to phosphate groups. The components of the electronic density of states were also analyzed, enabling us to identify correlations between the electronic structure and the structural properties, such as the different bonding character of Si-O bonds involving bridging or nonbridging oxygen atoms.