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Liquid lithography represents a robust technique for fabricating three-dimensional (3D) microstructures on a two-dimensional template. Silanization of a surface is often a key step in the liquid lithography process and is used to alter the surface energy of the substrate and, consequently, the shape of the 3D microfeatures produced. In this work, we present a passive technique that allows for the generation of silane gradients along the length of a substrate. The technique relies on a secondary diffusion chamber with a single opening, leading to a directional introduction of silane to the substrate via passive diffusion. The secondary chamber geometry influences the deposited gradient, which is shown to be well captured by Monte Carlo simulations that incorporate the passive diffusion and grafting processes. The technique ultimately allows the user to generate a range of substrate wettabilities on a single chip, enhancing throughput for organ-on-a-chip applications by mimicking the spatial variability of tissue topographies present in vivo.