The patterned alignment of liquid crystals is demonstrated on selectively thiol-functionalized photo-orientation layers (see cover). Deposited thiols are covalently bound to unsaturated linkages in linearly photo-polarizable materials, facilitating the simple and versatile combination of a bi-directionally planar and a homeotropic alignment of liquid crystals within a single substrate (e.g., in Figure). This opens new possibilities for the design, manufacture, and application of existing and novel display concepts.