It's time to talk about something that I'm very good at doing...stealing someone's girlfriend. Why do you need this skill? The majority of the hot women you meet will either be in relationships, or are mentally unstable.

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The only exceptions to this are hot women that are extremely busy with their careers (and aren't looking for boyfriends), hot women that are just now getting out of a relationship (very rare), and hot women that have exhausted the available decent men within their social circle (usually older hot women).
Here are the skills you need to steal hot women away from their boyfriends:
Penetrate Her Social Circle
As I've said time and time again, you have a significantly higher chance of dating a hot girl if you are a member of her social circle. Good luck stealing her if you're a stranger. This very rarely happens. When hot women leave their boyfriends/husbands, it's usually for another man that happens to be in her social circle of friends or work colleagues.
Befriend Her Friends
This is the key. Her friends will love to play matchmaker, and if they don't like her boyfriend, they're going to do whatever it takes to split them up. And if her friends like you, they're going to try to match you two up. And remember what I said about the friends of women? Women make their romantic choices based on what their friends tell them. So yeah, get in good with her friends.
Plant The Seed
If you're a member of her social circle and are tight with her friends, chances are, she's going to tell you about her relationship issues. First, you must learn to listen to her, thus encouraging her to always come to you with her relationship issues ("How are you and so and so doing?"). And when she does, cause her to question the validity of her relationship; point out all of her boyfriend's flaws, tell her that she deserves better, she's "smarter" than that etc. Play to her ego.
Be The Father Figure
This is how you will effectively make the transition from "let's just be friends" to "I want you". If you nail her on her flaws and mistakes, she will start to see you as an authority figure. And who do women want to date? The authority figures; teacher, boss, or in your case, the "big brother" that's always looking out for her and putting her in her place. I believe it is at this point that many of the women I was just "friends" with began to fall for me.
Pay Her No Special Attention
And what I mean by this, is that you shouldn't stop talking to other women. By now, she's going to start crushing on you, and when she knows that you have other options, she's going to become jealous and want you even more. You'll actually see an increase in the number of times she calls/texts you, and the frequency in which she wants to hang out.
Pull The Trigger
When you can tell that she's starting to see you as more than a friend, it is up to you to make the move. She's going to be giving you all kinds of signals that she wants you, if her friends haven't told you already, but since you're the authority figure, she's going to fear being rejected by you, so it is up to you to pull the trigger. She's either going to break up with her boyfriend, or be ready to do it as soon as she is sure that you share the same feelings that she has for you.
And like I said, I've done this with at least four or five of the girls that I've seriously dated, and it works like a charm.