Cayvan also acted at Booth's Theatre in New York City. She performed at the Fourteenth Street Theatre in "The White Slave" and Laura in "The Romany Rye." She also played Marcelle in "A Parisian Romance" in the Union Square Company. Cayvan was successful in the leading part of David Belasco’s "La Belle Russe." She was also a short time with Dion Boucicault.

In 1893 Cayvan became one of the first people to wear a glass dress. The dress was too brittle to be practical, however. It was exhibited at the World's Columbian Exposition in The Chicago's World's Fair of 1893. An article in The New York Times of July 28, 1893, predicted that glass dresses would become a fashion "fad." It points out that the first dress was made for Cayvan for her performance in "American Abroad." It was made by the Libbey Glass Company.  Author Amelia Ransome Neville in her book gave an account of seeing Cayvan wear the fiberglass dress made by Edward Drummond Libbey. She points out that Cayvan wore it in The Charity Ball.

In 1886 Cayvan contracted with Daniel Frohman, becoming the star of the Lyceum Theater in New York. Cayvan toured with her own company (which included Lionel Barrymore) starting in 1896. In March 1897, she performed with her company in El Paso, Texas in a production called "Squire Kate". She was involved in a difficult divorce case in 1896 as being the other woman. She was, however, totally exonerated after defending herself. Cayvan received much support from several women's groups.