A complexation of trimeric copper(i) and silver(i) 3,5-bis(trifluoromethyl)pyrazolates ((ML)3) with BH3NEt3 was studied by IR spectroscopy in hexane and dichloromethane solutions. In hexane, two complexes [(ML)3][BH3NEt3]2 (1) and [(ML)3][BH3NEt3] (2) were formed depending on the ratio of reagents. In dichloromethane, only one complex [(ML)3][BH3NEt3] (2) was found. The thermodynamic parameters (ΔH ○, ΔS ○) of complex 1 in hexane and complex 2 in dichloromethane were obtained. The complex [(AgL)3][BH3NEt3] was isolated in the solid state, its structure was established by X-ray diffraction. The complex is formed due to two bridges B-H-Ag, one BH group is not involved in the complexation. In crystal, molecules 2 form supramolecular dimers due to the intermolecular interactions between metals of two macrocycles.