The first sodium uranyl chromate, Na₄[(UO₂)(CrO ₄)₃], has been obtained by high-temperature solid-state reaction. The structure (triclinic, P1̄, Z = 2, a = 7.1548(3), b = 8.4420(3), c = 11.5102(5) Å, α = 80.203(1)°, β = 79.310(1)°, γ = 70.415(1)° V = 639.24(4) ų) has been solved by direct methods and refined on the basis of F² for all unique reflections to R1 = 0.024 [calculated on the basis of 4374 unique observed reflections (|F_o| ≥ 4σ_F)]. The structure is based on chains of composition [(UO₂)(CrO ₄)₃] that are parallel to [1̄01]. The chains contain UrO₅ pentagonal bipyramids (Ur = Uranyl) that share all equatorial corners with CrO₄ tetrahedra. Cr(1)O₄ and Cr(3)O ₄ tetrahedra bridge between two adjacent UrO₅ bipyramids, whereas Cr(2)O₄ tetrahedra share one corner with one UrO₅ bipyramid each. The [(UO₂)(CrO₄)₃] chains are planar and oriented parallel to (313). The Na⁺ cations provide linkage of the chains in the structure.