Metal-assisted Chemical Etching of silicon has recently emerged as a powerful technique to fabricate 1D, 2D, and 3D nanostructures in silicon with high feature fidelity. This work demonstrates that out-of-plane rotational catalysts utilizing polymer pinning structures can be designed with excellent control over rotation angle. A plastic deformation model was developed establishing that the catalyst is driven into the silicon substrate with a minimum pressure differential across the catalyst thickness of 0.4–0.6 MPa. Force–displacement curves were gathered between an Au tip and Si or SiO2 substrates under acidic conditions to show that Derjaguin and Landau, Verwey and Overbeek (DLVO) based forces are capable of providing restorative forces on the order of 0.2–0.3 nN with a calculated 11–18 MPa pressure differential across the catalyst. This work illustrates that out-of-plane rotational structures can be designed with controllable rotation and also suggests a new model for the driving force for catalyst motion based on DLVO theory. This process enables the facile fabrication of vertically aligned thin-film metallic structures and scalloped nanostructures in silicon for applications in 3D micro/nano-electromechanical systems, photonic devices, nanofluidics, etc.