New tetranuclear Cu(II) complex [Cu4(L)4]·MeCN (1) with 2,6-di(5-trifluoromethyl-1H-pyrazol-3-yl)pyridine (H2L) was synthesized. It has been shown that treatment of 1 with selected aza-ligands (pyridine, 2,2′- and 4,4′-bipyridyl, 2,3,5,6-tetra-(pyridine-2-yl)pyrazine, 2,2′;6′,2″-terpyridine and 1,4-diazabicyclo[2.2.2]octane) leads to formation of other Cu(II) complexes with different nuclearity: [Cu(L)py2] (2), [Cu(L)(2,2′-bpy)] (3), [Cu(L)2(tppz)]·THF (5), [Cu(L)tpy]·C6H5CN (4), {[Cu2(L)2(4,4′-bpy)2]·(C6H5CH3)·MeCN}n (6) and {[Cu(L)DABCO]·2MeCN}n (7). Obtained compounds were characterized by IR spectroscopy, X-ray crystallography data, EPR and SQUID magnetic measurements.