The dermocanarins 4-6 are unique naphthylanthraquinones containing a nine-membered lactone ring that have been isolated as the principal pigments of the subterranian mycelium of the fungus Dermocybe canaria and their structures determined by spectroscopic methods. In the fruit bodies of this fungus physcion 8-O-β-D-glucopyranoside 12 accompanies the aglycone 1 as the major colouring matters. In New Zealand Nothofagus forests Dermocybe canaria is a common species met within a remarkably wide ecological range. The toadstool is readily identified by the brilliant yellow colours of the rather robust fruit bodies and the dense mat of bright yellow mycelium from which the toadstools emanate. Air-dried fruit bodies of D. canaria collected by Horak in New Zealand were examined chemically by Keller and Steglich who found that the yellow anthraquinone physcion 1 is the most abundant pigment present, accompanied by lesser amounts of erythroglaucin 2 and the unique aminoanthraquinone 3. As part of our continuing studies on the constituents of Dermocybe species indigenous to Australia we have examined the pigments present both in the fresh fruit bodies and in the wild subterranian mycelium of D. canaria collected from Nothofagus forests in Tasmania, and also examined fresh specimens collected in New Zealand. We report here full details of the isolation, from the mycelium of D. canaria, of the first members of a new class of coupled octaketide pigments, the dermocanarins, in which anthraquinone and naphthalene moieties are linked both by a chiral biaryl bond and a lactone bridge. We have also found that in the fruit bodies of D. canaria physcion 1 and erythroglaucin 2 are accompanied by their respective 8-O-β-D-glucopyranosides. We have been unable to detect 4-aminophyscion 3 in either the mycelium or the fresh fruit bodies of D. canaria.