Munoz studied art at Washington and Lee University in Virginia. In 1950, she traveled up the Inside Passage by steamship, fell in love with Juneau, and gave herself until the boat left the next day to find a job and a place to live. Since then Juneau has been home to Munoz. She soon began painting small vignettes of Alaska, and also studied art at the University of Alaska-Juneau.
Munoz began painting in oils, but felt that it was somewhat boring. A friend introduced her to the inexpensive, water-soluble paint called casein and Rie’s paintings transformed into colorful and carefree depictions of the everyday life of Alaskans. Her paintings reflect an interest in the day-to-day activities of village life such as fishing, berry picking, children at play, as well as her love of folklore and legends.