Two novel chromium oxide arsenide materials have been synthesized, Sr2CrO2Cr2OAs2(i.e., Sr2Cr3As2O3) and Sr2CrO3CrAs (i.e., Sr2Cr2AsO3), both of which contain chromium ions in two distinct layers. Sr2CrO2Cr2OAs2was targeted following electron microscopy measurements on a related phase. It crystallizes in the space group P4/mmmand accommodates distorted CrO4As2octahedra containing Cr2+and distorted CrO2As4octahedra containing Cr3+. In contrast, Sr2CrO3CrAs incorporates Cr3+in CrO5square-pyramidal coordination in [Sr2CrO3]+layers and Cr2+ions in CrAs4tetrahedra in [CrAs]−layers and crystallizes in the space group P4/nmm. Powder neutron diffraction data reveal antiferromagnetic ordering in both compounds. In Sr2CrO3CrAs the Cr2+moments in the [CrAs]−layers exhibit long-range ordering, while the Cr3+moments in the [Sr2CrO3]+layers only exhibit short-range ordering. However, in Sr2CrO2Cr2OAs2, both the Cr2+moments in the CrO4As2environments and the Cr3+moments in the CrO2As4polyhedra are long-range-ordered below 530(10) K. Above this temperature, only the Cr3+moments are ordered with a Néel temperature slightly in excess of 600 K. A subtle structural change is evident in Sr2CrO2Cr2OAs2below the magnetic ordering transitions.