Electron Paramagnetic Resonance (EPR) techniques have been employed to investigate charge carrier trapping in the two main TiO2 polymorphs, anatase and rutile, with particular attention to the features of electron trapping sites (formally Ti(3+) ions). The classic CW-EPR technique in this case provides signals based on the g tensor only. Nevertheless a systematic analysis of the signals obtained in the various cases (anatase and rutile, surface and bulk centers, regular and defective sites) has been performed providing useful guidelines on a field affected by some confusion. The problem of the localization of the electron spin density has been tackled by means of Pulse-EPR hyperfine techniques on samples appositely enriched with (17)O. This approach has led to evidence of a substantial difference, in terms of wavefunction localization between anatase (electrons trapped in regular lattice sites exhibiting delocalized electron density) and rutile (interstitial sites showing localized electron density).