Two Ag+ complexes [Ag(HL)2(PF6)] (1) and [(AgL) n · n(CH2Cl2) · n(0.5H2O)] (2) (HL = 5-methyl-2-phenyl-4-[(2-o-tolylamino)-phenylmethylene]pyrazol-3(2H)-one) were synthesized and structurally characterized by EA analysis, IR spectra and X-ray crystallography. The result shows that two expected coordination modes (Modes I and III in Scheme 1) of the HL ligand, can be observed in its Ag+ complexes, while not in other transition metal ions (Ni2+, Co2+ or Cu2+) complexes whether deprotonation or not for the HL ligand. Three possible coordination modes (Modes I, II or III in Scheme 1) of the selected HL (HL = 5-methyl-2-phenyl-4-[(2-o-tolylamino)-phenylmethylene]pyrazol-3(2H)-one) ligand, can be adopted, in which Modes I and III can be observed in its two Ag+ complexes [Ag(HL)2(PF6)](1) and [(AgL) n · n(CH2Cl2) · n(0.5H2O)] (2), while Mode II just observed in its transition metal ions (Cu2+, Ni2+, or Co2+) complexes, resulting from the deprotonatd form of the HL ligand and the coordination characters of transition metal ions.