Two palladium(II) nitroaryl complexes trans-[bromo(p-nitrophenyl)bis(triphenylphosphine)palladium(II)] 1 and trans-[bromo(2,4-dinitrophenyl)bis(triphenylphosphine)palladium(II)] 2 have been synthesized. The complexes were characterized by FTIR and NMR (1H, 13C and 31P) spectroscopy and elemental analysis. The molecular structure of complex 2, as confirmed by X-ray crystallography, reveals that the Pd atom and its neighboring groups (two PPh3, Br and phenylene group) lie in a slightly distorted square plane. In the UV–Vis spectra of the complexes 1 and 2, the palladium to aryl charge transfer bands were observed. The emission peaks from the singlet excited states (S1 → S0) were observed in the photoluminescence spectra of the complexes. The thermal stability of the complexes has been studied by thermal gravimetric analysis (TGA). TGA data showed that both complexes are thermally stable up to 200 °C, and complex 1 is more stable than 2. The catalytic efficiency of the new palladium(II) complexes was studied as demonstrated using the Sonogashira coupling reactions with good yields. The experimental results suggest that the Sonogashira coupling reactions can be performed at moderate temperature (50 °C) using these new palladium(II) complexes as catalysts.