Abstract Volumetric solar receivers are essential components in high-temperature concentrated solar power plants. Their optical design is crucial for achieving efficient photon-thermal energy conversion; however, their three-dimensional geometry complicates a reliable and accurate optical characterization. This work proposes a new methodology for the 3D optical-performance analysis of the volumetric absorber having an open hierarchical structure. Firstly, the solar absorber is optically characterized using a test bench that mainly comprises a solar simulator and a customized instrument equipped with single-photon avalanche diodes, which holds the absorber and measures light flux on its external surface. Then experimental measurements are compared with a Monte Carlo ray-tracing numerical model. The results are consequently employed to understand light propagation in the absorber. This procedure is successfully applied to characterize a complex three-dimensional self-similar structure manufactured by Selective Laser Melting. The proposed experimental technique is a promising candidate for becoming a robust in operando method to characterize the radiation propagation within the complex porous structures employed for volumetric receivers.