Two new 3d–4f heterometallic coordination polymers, [Mn^IV₂Ce^IV₃O₆Na(OAc)₈(H₂O)₅](OH)·10H₂O (1) and [Mn^IINd^III₂Na₂(OAc)₈(H₂O)₆]·2(OH) (2) (OAc⁻ = acetate), have been conventionally synthesized and characterized by elemental analysis, IR, TG and single crystal X-ray diffraction. In 1, three Ce⁴⁺ and two Mn⁴⁺ cations are bridged by OAc⁻ and μ₃-O²⁻ bridges forming a pentanuclear 3d–4f heterometallic [Mn^IV₂Ce^IV₃O₆(OAc)₈(H₂O)₅] cluster, while in 2, two Nd³⁺ and one Mn²⁺ cations are linked by carboxylic bridge of OAc⁻ anions giving a 1D 3d–4f heterometallic [Mn^IINd^III₂(OAc)₈(H₂O)₆] chain. Additionally, pentanuclear heterometallic [Mn^IV₂Ce^IV₃O₆(OAc)₈(H₂O)₅] clusters in 1 are further connected by Na⁺ cations to result in a 1D chain, whereas the 3d–4f heterometallic chains in 2 are linked by Na1–O–Na1 dimers into a 2D array. Moreover, the variable magnetic susceptibilities of 1 and 2 are investigated.