Two special manganese complexes [Mn(II)(acac−)2(4,4′‐bipy)]n (bipy=4,4′‐bipyridine) (complex 1) and [Mn(III)(acac−)3]·4CO(NH2)2 (acacH=acetylacetone) (complex 2) were synthesized in the same strategy by solvothermal method. Single crystal X‐ray diffraction revealed the complex 1 consists of one‐dimensional infinite coordination chain, with the manganese centers bridged by 4,4′‐bipy. And free carbamides of complex 2 connect with each other through the hydrogen bonds to form a 14‐membered carbamide ring and a zig‐zag plane. Both enantiomers of Mn(III)(acac−)3 exist in the structure, forming a racemate. Furthermore, these enantiomers and those zig‐zag planes are linked with hydrogen bonds to form an unique spatial network.