Synthesis of a new family of air stable palladium(II)benzhydrazone complexes of the general formula [PdCl(PPh₃)(L)] (where HL = thiophene aldehyde benzhydrazones) incorporating PPh₃ and chloride as co-ligands has been described through a single and convenient step with good yields. All the new complexes have been fully characterized by means of elemental analysis, IR, UV-vis, and NMR spectral methods. The molecular structures of three of the complexes were determined by single crystal X-ray crystallography, which confirm the coordination mode of benzhydrazone and reveal the presence of a distorted square planar geometry around the Pd ion. The complexes 1–5 (0.05 mol%) have been found to be a highly active catalytic system in the mono and double Suzuki–Miyaura cross coupling reaction of deactivated aryl and heteroaryl bromides with different types of aryl boronic acids in neat water and the maximum yield was up to >99%. Notably, these catalysts work well with ultra-low loading of the catalysts and show high turnover numbers in a short time towards different substrates. Moreover, the catalysts could be simply recovered and reused five times without significant loss of efficiency.