from within the chroot wine works;

user@64studio:~$ wine 'C:\Program Files\Mozilla Firefox\firefox.exe'
Invoking /usr/lib/wine/wine.bin C:\Program Files\Mozilla Firefox\firefox.exe ...Wine failed with return code 1
/usr/bin/wine: line 533:  7971 Terminated              $XMESSAGE -timeout 30 -buttons "    Dismiss    ":0," Never display this message again ":3 -title "Wine Launch Window" -default "    Dismiss    " "Invoking $WINEBIN/$WINE_BIN_NAME $@ ...
        This dialog box is a temporary status dialog to let you know
        that Wine is attempting to launch your application.

        Since Wine is still very much in a development stage,
        many applications will fail silently.
        This dialog box is your indication
        that we're *trying* to run your application.

        This dialog box will automatically disappear after 30 seconds,
        or after your application finishes.

        You can permanently disable this dialog by selecting
        the option below.
        " 2>/dev/null



This is how i usually run 32 bit apps;

user@64studio:~$ dchroot -c ia32 -d wine 'C:\Program Files\Mozilla Firefox\firefox.exe'
I: [ia32 chroot] Running command: “wine C:\Program Files\Mozilla Firefox\firefox.exe”
Invoking /usr/lib/wine/wine.bin C:Program FilesMozilla Firefoxfirefox.exe ...
wine: cannot find 'C:Program'
Wine failed with return code 2

this is how my chroot is set up; http://www.crazysquirrel.com/computing/debian/amd64.jspx