Three α-pyrone derivatives, campyrones A-C (1-3), were isolated from Aspergillus niger, an endophytic fungus occurring in Zanthoxylum lemairei leaves. Their structures were elucidated by detailed spectroscopic and spectrometric analyses and confirmed by X-ray diffraction. The absolute configurations were assigned by a combination of circular dichroism spectra (CD) and X-ray analyses. Biosynthetically, pyrophen (4) and the new derivatives may be derived in a mixed biosynthesis from L-phenylalanine (for 4), L-isoleucine (for 1), L-leucine (for 2), and L-valine (for 3) as starter units, respectively. In bioassays, the new compounds exhibited weak toxicity on brine shrimp larvae (Artemia salina).