The crystal and molecular structures of the title compounds, [(o-tol)3PAu(6-MP)]·EtOH and [(c-hexyl)3PAu(6-Me-2-TU)], have been determined and each show the presence of a linear geometry about the Au atom; both of the thionucleobases function as thiolate ligands. Important interatomic parameters for [(o-tol)3PAu(6-MP)] are Au-S 2.266(2), Au-P 2.239(2) Å and S-Au-P 177.03(8)° and for [(c-hexyl)3PAu(6-Me-2-TU)]: Au-S 2.299(3), Au-P 2.244(3) Å and S-Au-P 176.1(1)°. Crystals of [(o-tol)3PAu(6-MP)]·EtOH are monoclinic with space groupP21/n, and unit cell dimensionsa=10.067(2),b=10.518(2),c=25.416(4) Å, ß=98.42(2)°,Z=4. The structure was refined to finalR=0.040 for 4183 data withI=3.0s(I). Crystals of [(c-hexyl)3PAu(6-Me-2-TU)] are monoclinic with space groupP21/c, and unit cell dimensionsa=9.692(4),b=15.822(4),c=15.775(3) Å, ß=94.00(2)°,Z=4,R=0.033 for 2666 data.