ABSTRACT We explore experimentally possible explanations of the polarization curves of the sunlight reflected by the Barbarian asteroids. Their peculiar polarization curves are characterized by a large-inversion angle, around 30°, which could be related to the presence of FeO-bearing spinel embedded in Calcium–Aluminum inclusions. In order to test this hypothesis, we have measured the phase function and degree of linear polarization of six samples of Mg-rich olivine and spinel. For each material, we have analysed the light scattering properties of a millimeter-sized grain and of two powdered samples with size distributions in the micrometer size range. The three spinel samples show a well-defined negative polarization branch with an inversion phase angle located around 24°–30°. In contrast, in the case of the olivine samples, the inversion angle is highly dependent on particle size and tends to decrease for larger sizes. We identify the macroscopic geometries as a possible explanation for the evident differences in the polarization curves between olivine and spinel millimeter samples. Although the polarization behaviour in near backscattering of the Barbara asteroid is similar to that of our spinel mm-sized sample in random orientation, this similarity could result in part from crystal retro-reflection rather than composition. This is part of an ongoing experimental project devoted to test separately several components of CV3-like meteorites, representative of the Barbarians composition, to disentangle their contributions to the polarization behaviour of these objects.