A new family of mixed-metal chalcogenides containing early rare-earth (RE) elements has been synthesized, e.g., Ca-4(RE)(2)In(4)Q(13) (RE = La, Nd, Sm, Gd; Q = S, Se). X-ray analysis showed that these compounds crystallize in an orthorhombic crystal system with the space group Pbam (No. 55); Z = 4. Four of the title compounds, being synthesized in single-crystal form via an eutectic halide flux method, were examined by X-ray single crystal diffraction methods. The indexed cell dimensions are a = 20.420 (3) Angstrom, b = 25.447 (6) Angstrom, and c = 3.934 (2) Angstrom for Ca4Nd2In4S13 (1), a = 21.348 (4) Angstrom, b = 26.562 (6) Angstrom, and c = 4.096 (3) Angstrom for Ca4Nd2In4Se13 (2) a = 21.348 (3) Angstrom, b = 26.483 (6) Angstrom, and c = 4.077 (2) Angstrom for Ca4Sm2In4Se13 (3), and a = 21.249 (3) Angstrom, b = 26.353 (5) Angstrom, c = 4.057 (3) Angstrom for Ca4Gd2In4Se13 (4). The structural and thermal parameters were refined by full-matrix least-squares methods to R/R(w)/GOF (based on F with 142 variables) = 0.040/0.047/1.39 (1), 0.040/0.043/1.27 (2), 0.036/0.041/1.31 (3), and 0.051/0.056/1.44 (4). The structure consists of cation-centered Ca-Q octahedra, (RE/Ca)-Q bicapped trigonal prisms, and In-Q tetrahedra and octahedra. Detailed studies reveal that these new phases are nonstoichiometric with respect to cation mixing, giving rise to a general formula of Ca-2+x(RE)(4-x)In(4)Q(13) (x similar to 2.0). The title compounds are isostructural with the Pb4In2Bi4S13 phase in the sense that the corresponding chemical formula can be written as (Bi2Pbx)Pb-4-x(In2Bi2)S-13 (x = 2) The results of differential thermal analysis suggest that these new chalcogenides melt congruently under vacuum. The anomalous lower thermal stability for sulfides compared to selenides observed in thermogravimetric analyses is attributed to an oxidative decomposition to complex sulfates at elevated temperatures. Preliminary optical bandgap measurements of selected phases show medium-gapped semiconductors with E(g) of similar to 2.0 eV for sulfides and similar to 1.2 eV for selenides. Structure and property comparisons between the CaYbInQ(4) and Ca-4(RE)(2)In(4)Q(13) families are briefly discussed.