 Data on the synthesis and study of the crystal structure of [Li10(Piv)10(MeCN)2]n (I) and [Li6(Piv)6(MeCN)2]n (II) are presented. According to X-ray diffraction data (CIF files CCDC nos. 1957855 (I); 1955569 (II)), compounds I and II are 1D polymers composed of deca- and hexanuclear fragments, respectively, in which the lithium atoms are linked to one another by μ3- and μ4-bridging pivalate anions.