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However, I suspect they feel uncomfortable
The time to tell a MILF she is a MILF is when you're having pillow talk. Of course by then she already knows you feel this way so it's pointless to call her this.
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maybe they are taken aback by the sudden change in mood. like one second I am being this harmless guy and the next second I am telling her she is a milf?
Yes by all means if you are going to call her a milf (i wouldn't do this) come with a sexy vibe and demeanor (come with this demeanor in any event unless you just want to be buddies and pals with the women you are approaching).
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to sum it all up, how do I tell a milf I am interested in her?
"You seem cool we should hang out let me take your number."