For simple renaming, it is not necessary to switch workspaces, unless the workspace you want to rename is not the one currently active.
Anyway, you can rename the current open workspace by choosing Eclipse->Preferences->General->Workspace and changing the option "Workspace name (shown in window title)" from the default's workspace folder name to whatever you want to call it. Then, restart Eclipse.
Suppose your workspace's folder is "/foo/bar/workspace" and you never changed its name before; its name was then the default "workspace". After you renamed it to, say, "my_workspace" and restarted Eclipse, the Eclipse's window title should show: "my_workspace - (some stuff that varies) - /foo/bar/workspace".
Note that this is NOT going to modify the workspace folder's name. You may have to create a new folder with the desired name, switch to that folder (whose workspace will have the same name, by default) and import existing projects into it, as some have suggested here.