The synthesis, spectroscopic characterization and thermal behavior of the pyrazolate-bridged palladium complexes [Pd3(µ-N3)(µ-Pz)5]n (1), [Pd3(µ-N3)(µ-mPz)5]n (2), [Pd3(µ-N3)(µ-IPz)5]n (3), [Pd6(µ-N3)2(µ-Pz)5(µ-mPz)5]n (4), [Pd6(µ-N3)2(µ-Pz)5(µ-dmPz)5]n (5) and [Pd6(µ-N3)2(µ-Pz)5(µ-IPz)5]n (6) {pyrazolate (Pz -), 4-methylpyrazolate (mPz -), 3,5-dimethylpyrazolate (dmPz -), 4-iodopyrazolate (IPz -)} have been described in this work. The thermal decomposition of the compounds occurs in four or five stages and the final decomposition residues were identified as metallic palladium using X-ray powder diffraction method. TG studies showed that the introduction of substituted pyrazolato groups in the composition of the polynuclear compounds affect significantly their thermal stability. It can be concluded that the presence of pyrazolato ligands containing methyl or iodine groups at the 4 position has a crucial effect on the thermal stability of the polynuclear compounds described in this work.