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A series of 4‐ethynylaniline gold(I) complexes containing monophosphane (1,3,5‐triaza‐7‐phosphaadamantane (pta; 2), 3,7‐diacetyl‐1,3,7‐triaza‐5‐phosphabicyclo[3.3.1]nonane (3), and PR₃, with R=naphthyl (4), phenyl (5), and ethyl (6)) and diphosphane (bis(diphenylphosphino)acetylene (dppa; 7), trans‐1,2‐bis(diphenylphosphino)ethene (dppet; 8), 1,2‐bis(diphenylphosphino)ethane (dppe; 9), and 1,3‐bis(diphenylphosphino)propane (dppp; 10)) ligands have been synthesized and their efficiency against tumor cells evaluated. The cytotoxicity of complexes 2–10 was evaluated in human colorectal (HCT116) and ovarian (A2780) carcinoma as well as in normal human fibroblasts. All the complexes showed a higher antiproliferative effect in A2780 cells, with the cytotoxicity decreasing in the following order 5>6=9=10>8>2>4>7>3. Complex 4 stands out for its very high selectivity towards ovarian carcinoma …