A series of luminescent bis-cyclometalated alkynylgold(III) complexes have been synthesized and characterized. Some of the complexes have been demonstrated to exhibit gelation properties driven by π-π stacking and hydrophobic-hydrophobic interactions. The gelation properties have been investigated in detail through variable-temperature UV-vis absorption and emission studies, and the morphology of the gels has also been characterized by scanning electron microscopy and transmission electron microscopy.