Volumetric 3D printing is revolutionizing the fabrication of functional 3D objects. It enables the production of highly complex cm³-scale objects with micrometer features within seconds. However, current advancements in volumetric 3D printing have primarily focused on radical-mediated polymerizations, which are highly non-selective and cannot be triggered independently from each other. Yet, the demand for diverse material properties in a single print has become ever clearer in-light of rising complexity in a plethora of fields such as tissue engineering, microfluidics, soft robotics and bioelectronics. To address the multi-material limitation of 3D printing, we herein pioneer an approach towards volumetric 3D printing by implementing highly selective and λ-orthogonal photochemical reactions based on an in-depth understanding of their wavelength-resolved reactivity. The implementation of precision photochemistry in volumetric 3D printing paves the way towards rapid multi-material printing of highly complex cm³-scale objects, which constitutes the focus of the current project.