The hyperfine features and thermal stability of a muonium (Mu)-related paramagnetic center were investigated in the SrTiO 3 perovskite titanate via muon spin rotation spectroscopy. The hyperfine coupling tensor of the paramagnetic center was found to have prominent dipolar characteristics, indicating that the electron spin density is dominantly distributed on a Ti site to form a small polaron near an ionized Mu + donor. Based on a hydrogen-Mu analogy, interstitial hydrogen is also expected to form such a polaronic center in the dilute doping limit. The small activation energy of 30(3) meV found for the thermal dissociation of the Mu + -polaron complex suggests that the strain energy required to distort the lattice is comparable to the electronic energy gained by localizing the electron.Electron doping into an archetypal perovskite titanate, SrTiO 3 , results in intriguing physical properties such as superconductivity 1 and ferromagnetism, 2 and can help form a two-dimensional (2D) electron gas system at the LaAlO 3 /SrTiO 3 heterointerface. 3,4 This makes electrondoped SrTiO 3 a promising material for emerging oxide electronics. For many of its applications, it is crucial to determine whether excess electrons form either free or trapped carriers. However, experimental studies on (La, Nb)-doped or oxygen-deficient SrTiO 3 seem contradictory on this point. Optical conductivity and dc transport measurements showed that excess electrons behave as free carriers or large polarons having bandlike characteristics. 5,6 On the other hand, photoemission spectroscopy (PES) studies revealed an incoherent in-gap state, which can be associated with small polarons, and its coexistence with a coherent delocalized state. 7 The Kondo effect observed in an electric field-effect-induced 2D electron system in SrTiO 3 also suggests the coexistence of free and trapped carriers. 8 Although many theoretical studies have been conducted to understand such puzzling phenomena, 9-11 the origin of the dual electron behavior in n-type SrTiO 3 remains unclear.Interstitial hydrogen (H i ) also serves as a shallow donor in SrTiO 3 . 12 PES measurements on a SrTiO 3 (001) surface exposed to hot atomic hydrogen showed both in-gap and delocalized states. 13 This implies that small polarons can also exist in H i -doped SrTiO 3 . However, little is known about the microscopic nature of hydrogen dopants and doped electrons in bulk SrTiO 3 except for some insight provided by infrared (IR) and polarized Raman scattering spectroscopies 14-16 and positive muon spin rotation (µ + SR) spectroscopy. 17,18 . Further experimental investigations are required to fully elucidate the role of H i in bulk SrTiO 3 and better understand the behavior of excess electrons in n-type SrTiO 3 . a) ito.takashi15@jaea.go.jp Since hydrogen and muonium (Mu: a µ + -e − bound state) have almost the same reduced mass, the µ + SR technique has been extensively used for the study of hydrogen-related defects in condensed matter. [17][18][19][20][21][22][23] In this letter, we report a d...