Two chain compounds built with anti–anti acetate bridged Mn^III₃O units, [Mn₃O(Clppz)₃(EtOH)₄(OAc)]_n (1) and [Mn₃O(Clppz)₃(EtOH)₂(OAc)]_n (2), were synthesized and characterized. The magnetic studies indicate that 1 is a single-chain magnet with two slow magnetization relaxation processes which has for the first time been found in this type of chain complex, while 2 shows a field-induced metamagnetic behavior. The quite different magnetic behaviors resulted from the different number of coordinated ethanol molecules on the Mn^III₃O unit, four ethanol molecules for 1, and two ethanol molecules for 2. The best fittings to the experimental magnetic susceptibilities gave J₁ = −2.72 cm⁻¹, J₂ = −4.34 cm⁻¹, zJ = 1.24 cm⁻¹ for 1 and J₁ = −5.91 cm⁻¹, J₂ = −0.98 cm⁻¹, zJ = 1.71 for 2 above 30 K. The positive zJ values indicate the presence of weak ferromagnetic interactions between the trinuclear units via acetate bridges in 1 and 2.