The heterometallic optical complexes [Cu 2 Co( S , S (+)cpse) 3 (H 2 O) 3 ] · 4H 2 O ( 1 ) and [Cu 2 Ni( S , S (+)cpse) 3 (H 2 O) 3 ] · 10H 2 O ( 2 ) were obtained from the mononuclear copper(II) compound by the addition of nickel(II) or cobalt(II) chlorides, where (H 2 cpse) is the acetyl amino alcohol derivative N‐[2‐hydroxy‐1( R )‐methyl‐2( R )‐phenylethyl]‐N‐methylglycine. In comparison with the homotrinuclear copper(II) compound [Cu 3 ( S , S (+)cpse) 3 (H 2 O) 3 ] · 8H 2 O reported previously, the substitution of a copper(II) atom by one cobalt(II) ion gave place to a heterotrinuclear compound 1 , which presents ferromagnetic‐antiferromagnetic behaviour. When substituting a copper(II) by a nickel(II) ion, the trinuclear compound 2 showed an antiferromagnetic coupling. The magnetic behaviour of the heterotrinuclear compounds is driven by the nature of the metal ion which was introduced in the copper(II) triangular array. The ligand and its coordination compounds were characterized by IR, UV‐Vis‐NIR. Their chemical was confirmed by photoelectron spectroscopy (XPS).