invoke(): Calls the button's callback, and returns what that function returns. Has no effect if the button is disabled or there is no callback.
Reference:
How to execute python tkinter button without clicking mouse [closed]
from Tkinter import *
import tkMessageBox
t = Tk()
def button1_click():
tkMessageBox.showinfo("Message", "Bang!")
def button2_click():
button1.invoke()
button1 = Button(t, text="Button 1", command=button1_click)
button1.pack()
button2 = Button(t, text="Button 2", command=button2_click)
button2.pack()
mainloop()