N-coordinate Pd2+ complexes [PdL2] (L: N-N-quinoline-8-yl-R-benzenesulfonamides) (6-10) and [PdL2] complexes assembled on multi-wall carbon nanotubes (MWCNTs) hybrid nanomaterials were fabricated and characterized by various techniques. The [PdL2] impregnated MWCNTs materials (11-15) were applied as a counter electrode (CE) catalyst for triiodide to iodide reduction reaction in the dye-sensitized solar cells (DSSC) and investigated electro-catalytic activities. The MWCNTs-supported [PdL2] CEs (11-15) are exhibits as Pt-free CE with good power conversion efficiencies (PCEs), and compared to platinum and bare MWCNTs CEs and the PCE of bare MWCNTs was clearly improved by means of [PdL2] complexes (6-10). The DSSCs based on the hybrid counter electrodes (CEs) (11-15) and bare MWCNTs are indicated a relative efficiency (n(rel)) of 64.27%, 54.07%, 53.75%, 51.52% 44.82% and 27.27% concerning a Pt CE control device set at 100%. The report emphasizes that [PdL2] impregnated MWCNTs type counter electrodes (CEs) (11-15) are promising as effectively catalyst in working device design, particularly taking into account the eco-friendly approach of the hybrids.