from Tkinter import *

root = Tk()
lab = Label(root)
lab.pack(expand=YES, fill=BOTH)

# add a photo
img = PhotoImage(file=r'D:\OldVaio\Website\public_html\python_snake_ora.gif')
lab.config(image=img)

# change window icon
root.wm_iconbitmap(r'C:\Python23\py.ico')           # <---
root.wm_title('Viewer')
mainloop()