The volatile copper(I) complexes (beta-diketonate)Cu(PMe3)n where beta-diketonate = hexafluoroacetylacetonate (hfac), trifluoroacetylacetonate (tfac), and acetylacetonate (acac) for n = 1 and 2 and beta-diketonate = dipivaloylmethanate (dpm) and dibenzoylmethanate (dbm) for n = 1 have been prepared in high yield. These species have been characterized by spectroscopy and by elemental analysis. A number of derivatives have been characterized by single-crystal X-ray diffraction. The compound (hfac)Cu(PMe3) crystallizes in the space group P1BAR with alpha = 10.801 (2) angstrom, b = 12.676 (3) angstrom, c = 14.946 (3) angstrom, alpha = 91.10 (3)-degrees, beta = 100.65 (3)-degrees, gamma = 94.06 (3)-degrees, Z = 6, R = 6.71%, and R(w) = 7.26% for 3751 reflections. The compound (dpm)Cu(PMe3) crystallizes in the space group P1BAR with a = 10.193 (3) angstrom, b = 12.059 (3) angstrom, c = 14.547 (3) angstrom, alpha = 96.40 (2)-degrees, beta = 91.54 (2)-degrees, gamma = 90.65 (2)-degrees, Z = 4, R = 5.34%, and R(w) = 5.57% for 5261 reflections. The compound (dbm)Cu(PMe3) crystallizes in the space group Cmc2(1) with a = 18.776 (6) angstrom, b = 7.995 (3) angstrom, c = 11.872 (4) angstrom, Z = 4, R = 2.72%, and R(w) = 2.83% for 1620 reflections. While (acac)Cu(PMe3) and (tfac)Cu(PMe3) have only limited thermal stability, (hfac)Cu(PMe3) is thermally stable for at least 4 days at its melting point (67-degrees-C). The vapor pressure of (hfac)Cu(PMe3) has been measured as a function of temperature, revealing reasonable volatility (100 mTorr at 60-degrees-C). From the plot of log (vapor pressure) versus reciprocal temperature, an enthalpy of vaporization (DELTA-H(vap)) of approximately 10 kcal/mol was obtained.