Two new polyketide-derived pigments, named rufoolivacins B (2), and D (4), with a 4′,10-coupled aryl linkage between polysubstituted 1-naphthol and 1,4- or 1,2-anthraquinone, together with nine known metabolites including rufoolivacins A (1) and C (3), have been isolated from the fruiting bodies of the Chinese toadstool Cortinarius rufo-olivaceus (basidiomycetes). Their structures were characterized on the basis of spectroscopic methods, including 2D-NMR experiments (COSY, NOESY, HSQC, and HMBC). The axial chirality of 1 and 2 was assigned through analysis of their CD spectra and ZINDO and TDDFT calculations. Compounds 3 and 4 were found to be unusual natural products incorporating an ortho-anthraquinone chromophore. All the metabolites were shown to be toxic toward the brine shrimp.