Slow magnetic relaxation is observed for [(tpa(Mes))Fe](-), a trigonal pyramidal complex of high-spin iron(II), providing the first example of a mononuclear transition metal complex that behaves as a single-molecule magnet. Dc magnetic susceptibility and magnetization measurements reveal a strong uniaxial magnetic anisotropy (D = -39.6 cm(-1)) acting on the S = 2 ground state of the molecule. Ac magnetic susceptibility measurements indicate the absence of slow relaxation under zero applied dc field as a result of quantum tunneling of the magnetization. Application of a 1500 Oe dc field initiates slow magnetic relaxation, which follows a thermally activated tunneling mechanism at high temperature to give an effective spin-reversal barrier of U(eff) = 42 cm(-1) and follows a temperature-independent tunneling mechanism at low temperature. In addition, the magnetic relaxation time shows a pronounced dc-field dependence, with a maximum occurring at approximately 1500 Oe.