I create a new Button object but did not specify the command option upon creation. Is there a way in Tkinter to change the command (onclick) function after the
Sure; just use the bind method to specify the callback after the button has been created. I've just written and tested the example below. You can find a nice tutorial on doing this at http://www.pythonware.com/library/tkinter/introduction/events-and-bindings.htm
from Tkinter import Tk, Button
root = Tk()
button = Button(root, text="Click Me!")
button.pack()
def callback(event):
print "Hello World!"
button.bind("", callback)
root.mainloop()