Silica monoliths with ordered arrays of micrometer-scale columns were fabricated from polyacrylamide gel templates. The preparation of the template involves the charged comonomer, N-acryloyl glycine, and is controlled by an externally applied electric field. This approach gives rise to the self-organization of columnar density patterns in the template (left; bar = 10μm) that are recovered in the silica monoliths upon impregnation with tetramethylorthosilicate and subsequent calcination (right).