“. . . You seem easier to get along with than your partner,” he noted. “After what happened in London, I wouldn’t have expected that.”
Wye shrugged. “It wasn’t your fault, what your partner did. Anyway, it’s all part of the spy trade, spies offing each other. That said, your Mr. Kuryakin ain’t one of my favorite people. I don’t take kindly to what he did, even if it is just par for the course. You already had Ecks caught; Kuryakin didn’t have to try to kill him.”
“Begging your pardon, but if the situation had been reversed, wouldn’t Mr. Ecks have done the same thing?” Napoleon replied. Even though he also felt Illya had been unnecessarily brutal during that incident, he was certainly going to examine the issue from all angles and not side against his partner along with the enemy.
“Well, now, you’ll have to ask him that,” Wye returned.
Napoleon gave a respectful nod. “Perhaps I shall.”
---The Peaceful Meadows Affair
In canon, Napoleon and Mr. Wye do not speak to each other. Wye does accidentally fire a shot at Napoleon and hit him when he chases the group onto the bus and Bryn hits him with her purse. He most likely would have fired deliberately at both Napoleon and Illya if given the chance; he was so furious and heartbroken about finding Mr. Ecks stabbed.
Napoleon and Mr. Wye don't interact as much as Illya and Mr. Ecks, nor are their exchanges anywhere as colorful. In his normal state of being, Mr. Wye is quite stable and calm and generally behaves as such with Napoleon. They get along in a fairly mature manner, discussing events and each other's partners and sometimes delving into deeper matters. Sometimes, however, Wye will instead behave in an amused or even a mocking way, depending on whether or not he doesn't want Napoleon to learn something in particular. This is more likely to occur if Illya is with Napoleon.
When Ecks was shot with a blaster gun after trying to protect Napoleon, Napoleon offered his assistance to Wye in trying to perform resuscitation. Napoleon felt he owed that to Ecks, and in addition, he didn't like to see Wye in agony over his friend's apparent death. Wye accepted his help, although neither was successful and it took Illya rewiring the gun to jump-start Ecks' heart again.
Later, as the group sat up to watch for any possible trouble, Wye volunteered a few small tidbits of information concerning himself and Ecks and their backstory. But, always one to be cautious in the spy trade, Wye was careful not to say much.
When the group was collectively called to Los Angeles to look for rogue Ms. Cue, Napoleon and Wye searched together and continued their traditionally mature conversations.