Держите. Если еще актуально…
import Image
import ImageTk
import Tkinter
#
def fill():
color = "#%02X%02X%02X" % (img_file.getpixel((100, 100)))
can_new["bg"] = color
#
root = Tkinter.Tk()
root.geometry("450x300+100+100")
#
can_old = Tkinter.Canvas(root, width=200, height=200, bd=2, relief="sunken")
can_old.place(relx=0.25, rely=0.45, anchor="center")
img_file = Image.open(r"d:\python27\foto.jpg")
img = ImageTk.PhotoImage(img_file)
can_old.create_image((104, 104), anchor="center", image=img)
#
can_new = Tkinter.Canvas(root, width=200, height=200, bd=2, relief="sunken")
can_new.place(relx=0.75, rely=0.45, anchor="center")
#
but = Tkinter.Button(root, text="Fill Right", command=fill)
but.place(relx=0.5, rely=0.9, anchor="center")
#
root.mainloop()
Файл foto.jpg приклеил…