The photophysical properties of a series of 4,6-diphenyl-2,2'-bipyridyl platinum(II) complexes bearing different sigma-alkynyl ancillary ligands (1a-1k) were systematically investigated. All complexes exhibit strong (1)pi,pi* absorption bands in the UV region; and broad, structureless charge-transfer band(s) in the visible region, which systematically red-shift(s) when the electron-donating ability of the para substituent on the phenylacetylide ligand increases. All complexes are emissive in solution at room temperature. When excited at the charge-transfer absorption band, the complexes exhibit long-lived orange emission (lambda(max): 555 601 nm), which is attributed to a triplet metal-to-ligand charge transfer/intraligand charge transfer emission ((MLCT)-M-3/(ILCT)-I-3). Most of these complexes exhibit broad triplet transient difference absorption in the visible to the near-IR region, with a lifetime comparable to those measured from the decay of the (MLCT)-M-3/(ILCT)-I-3 emission. The reverse saturable absorption (RSA) of these complexes were demonstrated at 532 nm using nanosecond laser pulses. The degree of RSA follows this trend: 1k approximate to 1a > 1c > 1f approximate to 1i > 1h approximate to 1b > 1e > 1d > 1g, which is mainly determined by the ratio of the triplet excited-state absorption cross section to that of the ground-state and the triplet excited-state quantum yield.