A new organically templated homochiral material (EMIm)[Co2-(D-cam)(2)(ac)] (1; D-H(2)cam = D-camphoric acid; ac = acetate; EMIm = 1-ethyl-3-methylimidazolium) has been ionothermally synthesized, and it features an unusual acetate-pillared cobalt-camphorate architecture encapsulating the cationic component of the ionic liquid.