Eight new complexes were synthesize d for the first time.The compounds which have the general formula K x H 2 [PM(OH 2 )Mo 7 W 2 V 2 O 39 ]·nH 2 O(M=Cr 3+ ,Mn 2+ ,Fe 3+ ,Co 3+ ,Ni 2+ ,Cu 2+ ,Zn 2+ ,Cd 2+ ;x=4or 5)were de-termined by conductance titration a nd elemental analysis.The analysis of IR,UV,XRD and ESR show that the products hold the Keggin structure a nd TG-DTA,IR,XRD at various tempera tures and water solubility test also give the evidences that the range of pyrolysis temperature is 300~350℃.T he study on the substitutional reaction of coordinated water by optical ligand quinine shows that the S N 2nucleophilic substitution occure s when Ni is con-tained in the compound and S N 1nucleophilic substitution occure s when Cu is contained.These also con firmed that the transitional metals are in the in ner sphere of the complexes.