Two copper(II) polymeric complexes {[Cu(HPymat)-(MeOH)](NO3)}(n) (1) and {[Cu-4(Pymab)(4)(H2O)(4)](NO3)(4)} (2) were synthesized with the carboxylate-containing Schiff-base ligands HPymat(-) and Pymab(-) [H(2)Pymat = (E)-2-(1-(pyridin-2-yl)-methyleneamino)terephthalic acid, HPyrnab = (E)-2-((pyridine-2-yl)methyleneamino)benzoic acid]. Complex 1 is a one-dimensional Cu(II) cationic polymeric complex containing free protonated carboxylic groups and nitrate anions as counterions. Complex 2 is a zero-dimensional tetranudear cationic Cu(11) complex containing nitrate anions as counterions. Complex 1 shows rhombic electron paramagnetic resonance (EPR) spectra in the solid state at room temperature (RT) and 77 K and tetragonal EPR spectra in dimethyl sulfoxide (DMSO) and dimethylformamide (DMF) and "inverse" EPR spectrum in CH3CN. Complex 2 shows rhombic EPR spectra in the solid state at RT and 77 K. But complex 2 shows tetragonal spectra in DMSO, DMF, and CH3CN. Thermogravimetric analysis was also performed for both complexes 1 and 2. Mean-square displacement amplitude analysis was carried out to detect librational disorder along the metal-ligand bonds in crystal structures.