Several cyclometalated ruthenium complexes 1–5 with 2-alkenylpyridines as C,N-chelating ligands were synthesized and then characterized by NMR, MS, IR and UV-Vis spectra. According to the single crystal of complex 2, it is evident that carbon from vinyl group is successfully bonded to Ru(II) center. Moreover, the Ru–N bond trans to the Ru–C bond is elongated (2.127(5) Å), which is consistent with the strong trans effect of the carbon atom compared to that of the nitrogen atom. With different electron-donating groups linked to vinyl, these complexes exhibited regular changes in MLCT absorption bands, which were identified by UV-Vis and CV spectra in combination with DFT and TD-DFT. Interestingly, protonated intermediate species of these complexes in acidic solutions were tracked by the absorption changes and MS spectra, which displayed a possible protonation process of these complexes with the cleavage of Ru–C σ bonds.