We report on a nanoscale quantum-sensing protocol which tracks a free precession of a single nuclear spin and is capable of estimating an azimuthal angle-a parameter which standard multipulse protocols cannot determine-of the target nucleus. Our protocol combines pulsed dynamic nuclear polarization, a phase-controlled radiofrequency pulse, and a multipulse AC sensing sequence with a modified readout pulse. Using a single nitrogen-vacancy center as a solid-state quantum sensor, we experimentally demonstrate this protocol on a single 13 C nuclear spin in diamond and uniquely determine the lattice site of the target nucleus. Our result paves the way for magnetic resonance imaging at the single-molecular level.Nuclear magnetic resonance (NMR) spectroscopy is an analytical technique extensively used in chemistry, biology, and medicine. It achieves sub-ppm spectral resolutions to provide a wealth of information on the structure and chemical environment of molecules, but requires at least nanoliter-volume analytes containing an ensemble of identical nuclei, due to the insensitive induction detection the technique relies on. In recent years, single isolated electron spins in solids, most prominently those associated with nitrogen-vacancy (NV) centers in diamond [1][2][3], have emerged as atomic-scale quantum sensors capable of detecting weakly-coupled external nuclei in as small as zeptoliter volumes: a dramatic decrease compared with conventional NMR [4][5][6]. Furthermore, various NMR protocols, in which a train of properly-timed microwave pulses interrogates precessing nuclear spins via the interaction with the sensor electron spin, have been devised and applied to external nuclei, demonstrating identifications of isotopes [7][8][9], detection of single protons [10], spectroscopy of single proteins [11], spectral resolution approaching that of conventional NMR [12,13], and so on [14][15][16][17]. A far-reaching yet natural goal of this line of research is chemical structure analysis at the single-molecular level, i.e., the determination of chemical identities and locations of the constituent nuclei in a single molecule.For nuclei dipolarly-coupled with a sensor, the knowledge of the hyperfine parameters A and A ⊥ (the parallel and perpendicular components, respectively) translates to the coordinate parameters r and θ, the distance from the sensor and the tilt (polar angle) from the applied static magnetic field B 0 , respectively, owing to the form of the interaction ∝ (3 cos 2 θ − 1)/r 3 or 3 cos θ sin θ/r 3 [ Fig. 1(a, left)]. 13 C nuclei (I = 1 2 ) in diamond sensed by the NV electronic spin (S = 1) have served as a canonical testbed for various NMR protocols to characterize the hyperfine parameters [3,[18][19][20][21][22][23][24][25]. For instance, in correlation spectroscopy, a multipulse sequence is repeated with the interval of t corr , during which a target nuclear spin evolves freely. Boss et al. demonstrated that, by engineering the Hamiltonian during the free nuclear precession, both A and A ⊥ can be estima...