Four pyridine-bridged bis(1,2,3-triazoles) A/B and C/D have been prepared by "click" reactions. Methylations/ethylations of A/B and C/D employing Meerwein's salts led to the formation of the corresponding dicationic salts 1/2 and 3/4 with pyridine moieties surviving from the alkylations. Interestingly, the reactions of "N-linked" salts 1/2 with K2CO3 in the presence of elemental sulfur did not yield the mesoionic carbene-sulfur betaine adducts but unexpectedly afforded 1,5-disubstituted triazoles 5/6, which may produce pyridine thioaldehydes as by-products. In contrast, in the case of "C-linked" salts 3/4, the reactions to synthesize carbene-sulfur zwitterions 9/10 proceeded smoothly. Employing a silver-carbene transfer protocol with salt 3 as the precursor, the [CNC]-type palladium pincer complex 8 was synthesized, the solid-state structure of which was determined by X-ray diffraction analysis. Complex 8 underwent ligand substitutions with silver carboxylates producing the acetato complex 11 and trifluoroacetato complex 12. All newly synthesized pincer complexes were employed to test their catalytic activities in Mizoroki-Heck reactions. Positive mercury drop tests implied that the pincer-type complexes do not survive under the conditions of catalysis, owing to which no conclusions can be drawn regarding the catalyst variation or substrate scope.