Reactive interface patterning promoted by lithographic electrochemistry serves as a facile method for generating submicron structures on conductive substrates. A binary‐potential step applied to a metal layer with a resist overlayer allows silicon to be patterned with metal oxides. In this study, the role and influence of the resist overlayer on the uniformity of pattern formation are examined. The ability of the resist to detach from the underlying metal is a critical determinant of pattern geometry. By choosing an appropriate resist, large patterns with submicron precision are generated quickly by the application of the binary‐potential steps. From this information, a lithography‐free approach to generating identical patterns is achieved with simple resists such as that furnished from a lacquer–water emulsion, thus greatly simplifying the patterning of silicon with metal oxide catalysts. Electrochemical surface‐patterning of silicon is achieved with a step potential to oxidize a metal substrate underneath a lithographic mask. Flexible lithographic masks allow for uniform and large metal oxide patterns with submicron precision. The approach is extended to patterning without the need for a lithographic mask. A lacquer–water emulsion serves as a mask and furnishes well‐defined patterns.