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The title compound, potassium silver tetra­niobium nona­oxide arsenate, K 0.8 Ag 0.2 Nb 4 O 9 AsO 4 , was prepared by a solid-state reaction at 1183 K. The structure consists of infinite (Nb 2 AsO 14 )  n   chains parallel to the  b  axis and cross-linked by corner sharing  via  pairs of edge-sharing octa­hedra. Each pair links together four infinite chains to form a three-dimensional framework. The K +  and Ag +  ions partially occupy several independent close positions in the inter­connected cavities delimited by the framework. K 0.8 Ag 0.2 Nb 4 O 9 AsO 4  is likely to exhibit fast alkali-ion mobility and ion-exchange properties. The Wyckoff symbols of special positions are as follows: one Nb 8 e , one Nb 8 g , As 4 c , two K 8 f , one Ag 8 f , one Ag 4 c , one O 8 g , one O 4 c .

K0.8Ag0.2Nb4O9AsO4

K_0.8Ag_0.2Nb₄O₉AsO₄