They work in the most dysfunctional way that makes the pairing so different from everything else you see.
That, and they've been at it for 400 years.
Another canon coupling that I adore is Peter/MJ. What saddens me is that the movies took the most awesome kickass woman and turned her into Lois Lane. I-just--WHY. The little details of MJ working on his costume, MJ defending Peter from other guys and girls, MJ who waits for him in the rain for their fancy date. The whole stress on the fact that Peter loved MJ in the movies felt a little too forced. Peter did love MJ, but MJ loved Peter more. Easily.
There's one short Spiderman story known as "Kiss of the Spiderwoman" where MJ makes a choice. It's a beautifully written story that semi-revolves around Gwen Stacy's death and MJ's role in Peter's life. Something I should upload and share one of these days.
Also, MJ should be loved for this line, "The reason I don't talk to pretty boys is because I have my own pretty boy."