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Tomographic volumetric printing (TVP) physically reverses tomography to offer fast and auxiliary-free 3D printing. Here we show that wavelength-sensitive photoresins can be cured using visible ($$\bar{\lambda }=455$$ λ ¯ = 455  nm) and UV ($$\bar{\lambda }=365$$ λ ¯ = 365  nm) sources simultaneously in a TVP setup to generate internal mechanical property gradients with high precision. We develop solutions of mixed acrylate and epoxy monomers and utilize the orthogonal chemistry between free radical and cationic polymerization to realize fully 3D stiffness control. The radial resolution of stiffness control is 300 µm or better and an average modulus gradient of 5 MPa/µm is achieved. We further show that the reactive transport of radical inhibitors defines a workpiece’s shape and limits the achievable stiffness contrast to a range from 127 MPa to 201 MPa according to standard tensile tests after post-processing. Our result presents a strategy for controlling the stiffness of material spatially in light-based volumetric additive manufacturing.

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