You can't use double quotes within other double quotes, so try to use single quotes for server attribute and double for Eval
<cms:CMSRepeater runat="server" ID="users" ClassNames="MySite.Users" TransformationName="MySite.Users.Default" Path='/<%# Eval("DocumentName") %>/%'></cms:CMSRepeater>
And use NodeName instead of DocumentName as Brenden said