Phase-pure samples and single crystals of the rareearth oxyselenides RE 4 Ga 2 Se 7 O 2 (RE = Pr, Nd) were prepared by reactions at 950 °C. They adopt a new structure type (orthorhombic, space group Pnma, a = 11.721(2)−11.683(2) Å, b = 3.9882(7)−3.9667(7) Å, c = 29.644(5)−29.581(5) Å, Z = 4) consisting of RESe 6 trigonal prisms, GaSe 4 tetrahedra, and GaSe 5 trigonal bipyramids linked to form corrugated layers between which strips of edge-sharing RE 4 O tetrahedra are inserted. The bonding character is mostly ionic within RE−O and RE−Se blocks but mostly covalent with Ga−Se blocks, as supported by electronic structure calculations. Both compounds show a nearly direct optical band gap of 1.7 eV. Their Seebeck coefficients and electrical conductivities are predicted to be similar to other oxychalcogenides, with the thermoelectric power factors being improved by ndoping. They exhibit high electrocatalytic performance for the oxygen evolution reaction, with the Pr member demonstrating superior activity, as characterized by a low overpotential of 257 mV (at a current density of 10 mA cm −2 ), a high mass activity of 70.1 A g −1 , and a turnover frequency of 0.0234 s −1 in 1 M KOH electrolyte.