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[en] Highlights: • Theory of Resonant Four-Wave Mixing. • Rotational and translational anisotropy of photolysis products. • Photolysis pathways. Based on the line-space quantum formalism, the potential of Resonant Four-Wave Mixing spectroscopy as a new tool to study rotational and translational anisotropy of photofragments produced by absorption of plane-polarized photons is theoretically addressed. Synergy of the flexible polarization setup, fine quantum state resolution and of the possibility to study translational recoil distributions, makes the tool unsurpassed among the all-optical means to interrogate the photofragment states. It allows to directly separate signals induced by the rotational anisotropy which remain silent in the most of laser-induced fluorescence responses and thus opens new ways to study rotational helicity, a crucial signature of the photolysis pathway.