LiVOPO4 is an attractive high-voltage cathode with rich polymorphs (α, β and αI). We present here a comparison of the behaviors of three LiVOPO4 polymorphs during delithiation/lithiation. Experimental and computational work suggests that α-LiVOPO4 suffers from more severe conductivity problems among the three forms. For the first time, our preliminary studies on lithiated β-Li2VOPO4 demonstrate that the orthorhombic structure of β-LiVOPO4 could be retained after lithiation, which is consistent with the finding for the other two forms.