A novel yellowish pigment, xanthouroleuconaphin, was isolated from the aphid Uroleucon nigrotuberculatum. Its structure was established by detailed analyses of 1D and 2D NMR spectra and EI-HRMS. Furthermore, the total synthesis of (±)-xanthouroleuconaphin was accomplished via oxidative phenolic coupling of 6-hydroxymusizin, which was prepared by the Fries rearrangement using BF3· 2AcOH complex.