Organic semiconductors are of interest for (opto)electronic applications due to their low cost, solution processability, and tunable properties. Recently, natural product-derived organic pigments attracted attention due to their extraordinary environmental stability and unexpectedly good optoelectronic performance, in spite of only partially conjugated molecular structure. Fungi-derived pigments are a naturally sourced, sustainable class of materials that are largely unexplored as organic semiconductor materials. We present a study of the optical and electronic properties of a fungi-derived pigment xylindein, which is secreted by the wood-staining fungi , and its blends with poly(methyl methacrylate) (PMMA) and crystalline nanocellulose (CNC). Optical absorption spectra of xylindein revealed the presence of two tautomers whose structures and properties were established using density functional theory. Pronounced pigment aggregation in polar solvents and in films, driven by intermolecular hydrogen bonding, was also observed. The pigment exhibited high photostability, electron mobility up to 0.4 cm/(V s) in amorphous films, and thermally activated charge transport and photoresponse with activation energies of ∼0.3 and 0.2 eV, respectively. The dark and photocurrents in xylindein:PMMA blends were comparable to those in pristine xylindein film, whereas blends with CNC exhibited lower currents due to inhomogeneous distribution of xylindein in the CNC.