The benzonitrile solvate {[{Au(C6F5)2}2{Pb(terpy)}]·NCPh}n (1) (terpy = 2,2':6',2″-terpyridine) displays reversible reorientation and coordination of the benzonitrile molecule to lead upon external stimuli. High-pressure X-ray diffraction studies between 0 and 2.1 GPa reveal a 100% of conversion without loss of symmetry, which is totally reversible upon decompression. By variable-temperature X-ray diffraction studies between 100 and 285 K, a partial coordination is achieved.