The structures and compositions of alluaudite-type double molybdates of sodium with scandium and indium are refined. The formulas Na5R(MoO4)4 (R = Sc, In) have previously been accepted for them, however, our new single crystal X-ray diffraction data show that their compositions noticeably differ from the initial ones: Na5.24Sc0.92(MoO4)4 = Na3.93Sc0.69(MoO4)3 (space group C2/c, Z = 4, a = 12.8911(6) Å, b = 13.9149(4) Å, c = 7.2544(3) Å, α = 113.011(2)°, R = 0.0212) and Na5.74In0.75(MoO4)4 = Na4.31In0.56(MoO4)3 (a = 12.8294(5) Å, b = 13.8906(5) Å, c = 7.2961(3) Å, β = 112.729(1)°, R = 0.0164). This indicates the nonstoichiometry of the studied crystals. Their compositions as well as initial Na5R(MoO4)4 = Na3.75R0.75(MoO4)3 are close to the opposite boundaries of homogeneity regions found near the melting points of double molybdates Na3+3xR1−x(MoO4)3 (R = Sc, In) which are 0.25 ≤ x ≤ 0.35 (R = Sc) and 0.25 ≤ x ≤ 0.45 (R = In). They are consistent with the general formula Na9−3xR1+x3+(MoO4)6 that we have previously proposed for alluaudite-type double molybdates of sodium and trivalent metals. The characteristic features of both structures are a partial occupancy of all three crystallographic sites of sodium along with the presence of the mixed octahedral site (Na, R), where R = Sc, In. The features of the crystal structures of the studied compounds, calculations of bond-valence sum maps, and also the previously obtained data of solid-state NMR and non-empirical calculations indicate the predominantly one-dimensional, as in the other alluaudites, character of the sodium ion transport through the chain of Na(3)–Na(3) polyhedra along the c axis. However, at elevated temperatures a two-dimensional conductivity is possible in the (100) plane due to the bridging positions of Na(1) and Na(2).