Bose-Einstein condensates have been prepared in long-lived metastable excited states. Two complementary types of metastable states were observed. The first is due to the immiscibility of multiple components in the condensate, and the second to local suppression of spin-relaxation collisions. Relaxation via re-condensation of non-condensed atoms, spin relaxation, and quantum tunneling was observed. These experiments were done with F = 1 spinor Bose-Einstein condensates of sodium confined in an optical dipole trap.Metastable states of matter, excited states which relax only slowly to the ground state, are commonly encountered. This slow relaxation often arises from the presence of free-energy barriers that prevent a system from directly evolving toward its ground state; if the thermal energy to overcome this barrier is not available, the metastable state may be long-lived.Many properties of Bose-Einstein condensates in dilute atomic gases [1][2][3][4] arise from metastability; indeed, such condensates are themselves metastable, since the true equilibrium state is a solid at these low temperatures. Bose-Einstein condensates in gases with attractive interactions (scattering length a < 0) [3] are metastable against collapse due to a kinetic energy barrier [5]. The persistence of rotations in condensates with repulsive interactions (a > 0) hinges on whether vortices are metastable in singly- [6] or multiply-connected [7,8] geometries. Similarly, dark solitons in restricted geometries are predicted to be long-lived [9] akin to the recently observed metastable states in superfluid 3 He-B [10]. Finally, Pu and Bigelow discussed spatial distributions of two-species condensates which are metastable due to mean-field repulsion between the two species [11].In this Letter, we report on the observation of two complementary types of metastability in F = 1 spinor Bose-Einstein condensates of sodium. In one, a twocomponent condensate in the |F = 1, m F = 1, 0 hyperfine states was stable in spin composition, but spontaneously formed a metastable spatial arrangement of spin domains. In the other, a single component |m F = 0 condensate was metastable in spin composition with respect to the development of |m F = ±1 ground-state spin domains. In both cases, the energy barriers which caused the metastability (as low as 0.1 nK) were much smaller than the temperature of the gas (about 100 nK) which would suggest a rapid thermal relaxation. However, this thermal relaxation was slowed considerably due to the high condensate fraction and the extreme diluteness of the non-condensed cloud.Spinor Bose-Einstein condensates were created as in previous work [12]. Condensates in the |F = 1, m F = −1 state were created in a magnetic trap [13] and then transfered to an optical dipole trap formed by a single infrared laser beam [14]. The beam was weakly focused, producing cigar-shaped traps with depths of 1 -2 µK, radial trap frequencies of about 500 Hz, and aspect ratios of about 70. After transfer, Landau-Zener rf-sweeps placed the optically trappe...