Tkinter isn't exactly the most powerful of toolkits (it's very, VERY basic).
I'm not aware of something so simple in Tkinter, but you can do this:
w = root.winfo_screenwidth()
h = root.winfo_screenheight()
rootsize = tuple(int(_) for _ in root.geometry().split('+')[0].split('x'))
x = w/2 - rootsize[0]/2
y = h/2 - rootsize[1]/2
root.geometry("%dx%d+%d+%d" % (rootsize + (x, y)))
pyGTK OTOH is much better:
import pygtk
import gtk
win = gtk.Window(gtk.TOPLEVEL)
win.resize(300, 300)
win.set_position(gtk.WIN_POS_CENTER)
win.show()
Basically, Tkinter is good for a cheap and easy GUI - but it won't look that pretty without some serious work. The more advanced toolkits (pyGTK, PyQT) are a lot "prettier", but not as common, as Tkinter usually comes bundled with python. So if you want a pretty GUI, use a better toolkit, but if you just want something cheap and easy, use Tk.