But this collaboration especially hit home, says the star.
"The fragrances capture my own personal philosophy on life. Their names -- Laugh Often, Live Without Regrets and Love To The Fullest -- these are all words I live by," said Witherspoon.
Created to express the different moods of women, the Expressions collection will make its debut in April with Laugh Often's mix of juicy mandarin and fragrant freesia. Live Without Regrets will follow in May with a warm weather-friendly floral fruity flavor, and Love To The Fullest will round out the series in August, with an oriental blend of amber, woods, plush peony and a hint of sweet black cherry.
A self-described "lover of fragrances," Witherspoon said she jumped at the opportunity to create a trio of scents all at one time. The star credits the closest women in her life with endowing her with the passion to spritz.
"I remember my grandmother giving me the last bit of her perfume bottle, and pretending I was all grown up when I played with it. My mother also wore this beautiful gardenia perfume when we went on vacation. I always admired her, and thought she was the most beautiful woman in the world," said Witherspoon.
Yet just like food palettes, fragrance preferences can change dramatically throughout a woman's life. Chances are, the scent you doused in during your high school years is one that now repels you like opposite sides of a magnet.
Witherspoon revealed that she would buy anything and everything vanilla as a girl, but her preference has since shifted to white flowers sparked by citrus notes in recent years, a combination she happened upon while working with talented perfumers on her fragrance creations.
And, as in Hollywood, the outside packaging counts.
"I think it's important how they look on your vanity. Fragrance is such an expression of being a woman," said Witherspoon.
Not just a face of fragrance, the New Orleans native is also a global ambassador and the first honorary chairman of The Avon Foundation. As a part of her duties, Witherspoon embarks on worldwide travel advocating on behalf of women's issues -- most prominently, domestic violence.
In fact, Witherspoon says a woman she met on one such trip forever changed her life.
"I met a woman in Brazil -- Maria da Penha -- who was in a terrible relationship mired in violence with her husband of over 20 years. She had no legal recourse, and could find no help. It was such a dangerous situation that her husband finally shot and paralyzed her," Witherspoon said of the now paraplegic woman.
"She came forward and told her story, and they enacted a law in Brazil named after her that will change so many women's lives in Brazil, and around the world. She's a personal hero of mine," said Witherspoon.
Passed in 2006, the law no longer allows for domestic abusers to be served with "alternative sentences.: Instead, compulsory jail time and the removal of benefits like child custody can now be legal consequences in domestic violence cases.
It's precisely this kind of potential influence on women's lives that Witherspoon said tempted her into the worlds of acting and beauty spokesperson work.
"I became an actress because I wanted to express women's stories. I wanted to play strong, interesting, creative characters that represented the women I knew in real life. As an extension of that, I've worked with children's charities, which are my first passion. But I've discovered that when you empower children's mothers, that's when you're going to really change children's lives," said Witherspoon.
"That's all we can hope to do in life -- improve the lives of others. I feel that's my responsibility. I've been very lucky in life, and I want to share some of that."
And lucky for us, Witherspoon also possesses a flair for fashion. Check out pictures of her style evolution here.