In an attempt to perform a simple anion-exchange reaction on a pincer-carbene-ligated nickel complex using AgNO3, we instead obtained an unexpected three-dimensional (3D) Ag-7 cluster containing a [Ag-6] core in a twisted-bowtie geometry. The reverse-transmetalation reaction by which the carbene is transferred from nickel to silver is virtually unprecedented. The CNC pincer-carbene ligands exhibit unusual bridging modes of ligand bonding for all three donor atoms. Another unique feature is that the final structure exhibits a 3D structure brought about by the connection of two-dimensional layers of the [Ag-6] core via a seventh Ag ion.