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From what we can tell, Madame de Rênal has lived most of her life without really wondering what true love is. She has always done what society has told her, and as a result, she has become an admirable woman in the eyes of many townsfolk. As the narrator informs us,
She was a tall, well-made woman, who had been the local beauty, as people in these mountains put it. There was a distinct straightforwardness about her, and in the youthful spring of her walk. (1.3.27)
At the same time, Madame de Rênal has a modesty to her that definitely attracts a young idealistic kid like Julien Sorel. We find out early on that:
[In] the eyes of the town's ladies, she was an outright fool, since with not the slightest regard for proper management of her husband, she passed over the loveliest opportunities for buying beautiful hats from Paris or Besançon. (1.3.28)
In other words, Madame isn't as superficial as many of the women around her. And this can only look great to someone like Julien, who feels bitter about how shallow most people are.
With all of this upright behavior, it shouldn't surprise us that Madame doesn't give in to Julien's first romantic advances. At one point, he tries to hold her hand, but it doesn't go so well:
[He] put out his hand and grasped Madame de Rênal's, which was immediately withdrawn. (1.9.9)
Little does Madame know, though, that she's slowly becoming aware of what true passion is. And once she tastes its fruits, there's no going back.
Over time, Madame de Rênal realizes that she's in love with Julien and that she wants to become romantically involved with him. She knows how much she's risking her reputation, but what she doesn't know is how obvious her infatuation is becoming to others. Her cousin Madame Derville, for example, notices a stark change in the way Madame dresses:
Madame Derville had seen with great surprise that her friend, always criticized by Monsieur de Rênal for the plainness with which she dressed, had begun to wear fishnet stockings and delightful little shoes, fresh from Paris. (1.13.7)
It's true that Madame has always dressed plainly for her husband. But now she's dressing for someone else's eye… and she pulls out all the stops.
After she's had sex with Julien, Madame de Rênal realizes that she has crossed the line. She's a devoutly religious person, so she worries about going to hell. But she still can't help but act on her love for Julien. As she tells him toward the end of the book,
The boundaries of strict modesty have been crossed… I am a woman without honor and, truly, it has been for you. (2.43.36)
And one last thing: this woman is loving 'til the bitter, bitter end: even after Julien has tried to kill her, she loves him. That's not just romantic, that's ridiculously romantic. No one gets to say that our Madame isn't faithful in her love to Julien… even if he really doesn't deserve it.