That's easy. Just paste the jpeg into a new rgba Image()
:
#!/usr/bin/env python3
from PIL import Image
from PIL import ImageDraw
im = Image.open("existing.jpg")
logo = Image.open("python-32.png")
back = Image.new('RGBA', im.size)
back.paste(im)
poly = Image.new('RGBA', (512,512))
pdraw = ImageDraw.Draw(poly)
pdraw.polygon([(128,128),(384,384),(128,384),(384,128)],
fill=(255,255,255,127),outline=(255,255,255,255))
back.paste(poly, (0,0), mask=poly)
back.paste(logo, (im.size[0]-logo.size[0], im.size[1]-logo.size[1]), mask=logo)
back.show()
This additionally adds a png (with transparency) to the image.