Aryl bromides and 4-chlorotoluene as an example aryl chloride in the presence of N-heterocyclic carbene (NHC) palladium hydroxo dimers of the type [{Pd(µ-OH)Cl(NHC)}2] (where NHC = IPr, SIPr, IMes, SIMes) undergo an efficient and selective Sonogashira cross-coupling with (hetero)arylacetylenes. The procedure allows the high-throughput and selective synthesis of a broad spectrum of 1,2-diarylacetylenes using 10 ppm of [{Pd(OH)Cl(IPr)}2] as precatalyst. For the coupling of 4-chlorotoluene with phenylacetylene, TON = 560000 was achieved. Hydrogen chloride was observed as a product of the Sonogashira cross-coupling reaction. The formation of the active Pd(0) from the Pd(II) complex was found to proceed via ethanol oxidation. Mechanistic studies showed that water plays a key role in the reaction.