The fluorinated bis(pyrazolyl)borate [H2B(3,5-(CF3)2Pz)2]− allows the isolation of thermally stable copper(I) complexes containing phosphorus and nitrogen based donors, alkyne and alkene ligands. [H2B(3,5-(CF3)2Pz)2]Cu(PPh3), [H2B(3,5-(CF3)2Pz)2]Cu(NCCH3) and {[H2B(3,5-(CF3)2Pz)2]Cu}2(1,5-COD) were synthesized by using [H2B(3,5-(CF3)2Pz)2]K, CF3SO3Cu, and the appropriate ligand, PPh3, NCCH3 or 1,5-COD. [H2B(3,5-(CF3)2Pz)2]Cu(HC≡CPh) and [H2B(3,5-(CF3)2Pz)2]Cu(H2C=CHPh) were obtained by treating [H2B(3,5-(CF3)2Pz) 2]Cu(NCCH3) with phenylacetylene and styrene, respectively. X-ray data show that [H2B(3,5-(CF3)2Pz)2]CuL (where L = PPh3, HCCPh, H2C=CHPh) and {[H2B(3,5-(CF3)2Pz)2]Cu}2(1,5-COD) have three-coordinate, trigonal planar copper sites. The bis(pyrazolyl)borate moiety adopts the common boat conformation. The νC≡C stretching band of [H2B(3,5-(CF3)2Pz)2]Cu(PhC≡CH) was observed at 1927 cm−1. Structural and spectroscopic data of the alkene and alkyne complexes indicate minimal back-bonding from the d10 copper(I) center. [Copyright &y& Elsevier]