Just watched NEVER-NEVER again...
...and was struck anew at how sweet Napoleon really was with Mandy, understanding her want of excitement and trying that little ploy to give her some. (And he never flirts with her in the episode, though she gives him the perfect opening to do so when she suggests using her vacation time to be in Rio at the same time he will be there on a mission. Still, he doesn't rise to that bait and just treats her like a friend -- a somewhat frustrating friend, but still a friend.)
Yes, Napoleon's little gambit wasn't the wisest thing to do. But then again he didn't expect Mandy to get a hold of the microdot. (And why didn't that U.N.C.L.E. microdot creator ask for any kind of confirmation that she was indeed the courier before handing that over to her? Rather bad U.N.C.L.E. policy there.) Napoleon just thought she would go to the tobacco shop and get the pipe tobacco for Waverly, innocently thinking all the time that she was doing something secret agenty though she was in reality perfectly safe. That the itch would be scratched, so to speak.
And the bravado with firing the shot with his hands handcuffed behind him and only a mirror and a prayer to guide the shot: so Napoleon. And his own amazed wonder at his success afterwards: also sweet.
I also have to note here that, like in most of the first season episodes, many of the photographic choices in this episode were simply exquisite. I was particularly impressed in the fight scene in the garage where the Thrush grabs that blow torch and we see the flame reflected in Napoleon's eyes with a definite undercurrent of fear, and then later -- when the positions are literally reversed as Napoleon is holding the lighter up to the guy after dousing him with gasoline -- how we again see the flame reflected in Napoleon's eyes only now with an expression of sheer menace there. Brilliantly filmed.
I love this episode and I love the understanding side of Napoleon it so reveals.
Oh, and we also see in this episode that Napoleon's office is his own, not shared with Illya. We also see this in several other episodes as well: ALEXANDER THE GREATER and another when he is going over paperwork with his secretary while Illya is out on a mission -- that was the one where he is investigating what happens to "retired" lower-echelon Thrush, but the name of the episode is escaping me at the moment. So presumably both he and Illya have their own offices. I have to say this makes more sense to me since Napoleon is CEA and likely would have to hold meetings with various Section II agents going out on missions or reporting back on them (as well as give performance reviews); thus making a shared office a real inconvenience.