In issue #69 (written by Gail Simone), Deadpools secretary Sandi winds up in the hospital due to her abusive boyfriend. When Deadpool finds out about it, he makes sure to teach the guy some manners◊. Even better, Deadpool makes it abundantly clear that the only reason he kept said boyfriend alive is because Sandi asked him to - otherwise, he would have killed him for what he did.
Another Simone one had Deadpool force Black Swan to fix Ratbag's broken mind. It worked◊, and he got to be The Hero in his final issue.
Back in the Joe Kelly days, Deadpool had a heartwarming moment with Bullseye of all people. Bullseye gave Deadpool a heart to heart when he was in a slump... Well, as close as a heart to heart two Psychos For Hire can have. Check it out.
Also, back when Deadpool sorta died, Bullseye went to his funeral. D'awww.
And Bullseye actually shed a tear◊ when they said goodbye for the last time.
Deadpools heart-to-heart with Evan in the last issue of X-Force. Evan was upset about being Apocalypse's clone and that the life he thought he had was just a simulation, but Deadpool set him straight on both counts and told him he was the kind of kid he'd want his own son to be like.
Deadpool is the one who's shocked at what happens to Kid!Apocalypse in X-Force. Deadpool.
In Suicide Kings, during a fight between Deadpool and the Punisher that ended up wrecking Outlaw's house, Deadpool, with the cash he had on hand, ended up getting her a new place that wasn't full of Deadpool-sized holes and Punisher sweat. Needless to say, she was incredibly grateful. She ended up having sex with him to repay the favor, but hey, it's the smaller things that count.
And he paid for it with a Hamilton he got from an adorable little tyke who confused him for Spider-Man on the subway. When Deadpool told her that he had no money for cab fare, she happily made a donation◊.
In Vol. 5 issue #20, Deadpool interrupts a girl about to jump off of his apartment building and talk her into seeing Hamilton before dropping her off at the hospital to get her some help, revealing that this had been his plan all along and he had been texting the staff the whole time.
Deadpool getting married to Shiklah. Then when they honeymooned in New York, they ate hotdogs, caught (the first inning) of a game at Yankee Stadium, killed bad guys, escaped from police custody, visited Lady Liberty...
Shiklah just loves ol' Deadpool. When Deadpool was having bad dreams about Butler coming back and something bad happening to Ellie, and she dispelled them with mystical mojo and sweet words.
In Deadpool Annual #2, Spider-Man was facing a near endless onslaught of attacks by the Chameleon (who was disguising himself as random civilians) and was suffering from both sleep deprivation and paranoia. So when he collapsed, not only did Deadpool stop a bunch of crooks looking to unmask him for a reward, but also took his place for the day and made sure to follow his moral code while protecting the city.
The moment that Deadpool finds out that someone wants to harm his daughter, Ellie, nothing in the world stops him from making it to Chicago to save her. Not vampire hunting, not the distance from New York, and certainly not Flagsmasher.
Also when Deadpool brings Spider-Man along to meet Ellie. Ellie comes out to greet Deadpool, just knowing when he would show up, and they share a warm hug while she tells him about her week.
In Deadpool's Secret Secret Wars, when the Battleworld was granting everyone's wishes, instead of wising for the cure for cancer, he wished for Zsaji to be revived and sent to a far-off world where no other superheroes and Secret Wars would hurt her ever again.
Deadpool's relationship with the half clone of him, half clone of Squirrel Girl (long story). Especially when you compare it to the relationship he has with the other half clone of him, half clone of Spider-Man.