This study focuses on the exploration of the ternary systems A-Li-Pn with A = Ca-Ba, Eu and Yb and Pn = As-Bi resulting in the extensions of the ALiPn series (A = Ca, Sr, Eu and Yb; Pn = As-Bi; orthorhombic Pnma) with the MgSrSi structure type and of the A3Li4Pn4 family (A = Ba, Eu; Pn = As-Bi; orthorhombic Immm) with the Zr3Cu4Si4 structure type, as well as the novel compound Eu4Li7Bi6 (monoclinic, C2/m) with its own structure type. The relevant structural relationships are discussed. The building blocks and the topology of the polyanionic networks among the three different structures are compared side-by-side. Electronic band structure calculations for EuLiSb, Eu3Li4Sb4 and Eu4Li7Bi6 are discussed; the magnetic susceptibility and resistivity of single-crystalline Eu3Li4Sb4 are also presented.