The silicon-vacancy (SiV − ) color center in diamond has attracted attention because of its unique optical properties. It exhibits spectral stability and indistinguishability that facilitate efficient generation of photons capable of demonstrating quantum interference. Here we show optical initialization and readout of electronic spin in a single SiV − center with a spin relaxation time of T 1 ¼ 2.4 AE 0.2 ms. Coherent population trapping (CPT) is used to demonstrate coherent preparation of dark superposition states with a spin coherence time of T ⋆ 2 ¼ 35 AE 3 ns. This is fundamentally limited by orbital relaxation, and an understanding of this process opens the way to extend coherence by engineering interactions with phonons. Hyperfine structure is observed in CPT measurements with the 29 Si isotope which allows access to nuclear spin. These results establish the SiV − center as a solid-state spin-photon interface. DOI: 10.1103/PhysRevLett.113.263602 PACS numbers: 42.50.Gy, 03.67.Lx, 42.50.Ex, 61.72.jn Coherent quantum systems which efficiently couple long-lived quantum memories to optical photons are a key resource for realizing quantum networks [1]. Color centers in diamond [2] are attractive candidates owing to unique properties of diamond, which include optical transparency and a high lattice quality that allows spin to function as long-lived quantum memory [3]. The negative silicon-vacancy (SiV − ) defect in diamond [4-6] has exceptional optical properties that facilitate efficient generation of indistinguishable photons from multiple distinct emitters [7]. Here we show optical initialization and readout of electronic spin in a single SiV − center with a spin relaxation time of T 1 ¼ 2.4 AE 0.2 ms. Two-photon resonance [8] is used to demonstrate coherent preparation of dark superposition states with a spin coherence time of T ⋆ 2 ¼ 35 AE 3 ns. This is shown to be limited by orbital relaxation that may be suppressed by engineering interactions with phonons. We present the first evidence of hyperfine interaction with a 29 Si nuclear spin in SiV − which can potentially be used as a memory qubit [9].Quantum information processing efforts in diamond have mainly focused on the nitrogen-vacancy (NV − ) center because of its excellent spin properties at ambient conditions [10]. All-optical access to NV − spin is possible [11][12][13][14]; however, its large phonon sideband and spectral diffusion reduce coherent photon generation rates and limit the development of NV − quantum networks [15][16][17]. The main optical advantage provided by the SiV − center is that 70% of its fluorescence is concentrated in a sharp zero-phonon line (ZPL), making it ideal for single photon source applications [18,19]. It is spectrally stable at 737 nm, exhibits line widths limited by the excited state lifetime [20], and can be coupled to optical cavities [21,22]. Physically, the SiV − center consists of a single silicon atom replacing two carbon atoms in the diamond lattice, forming D 3d symmetry as illustrated in Fig. 1(a) [4][5]...