Charlene Doofenshmirtz (Allison Janney) is the former wife of Dr. Heinz Doofenshmirtz and shares custody of their daughter, Vanessa. She didn't divorce Heinz because he was evil; in her words, they just didn't get along very well and wanted different things. Whenever Vanessa tries to tell her that Heinz is actually evil, Charlene is adamant that no one can be evil. In contrast to Heinz's obvious agitation with her, she is actually very civil in his presence and talks of and to him as if they were still on relatively good terms ("I Scream, You Scream", "Hail Doofania!")
With the revelation that Charlene and Linda know each other, there has been speculation online about how much the Doofenshmirtz's and the Flynn-Fletcher's know each other. None of this has made it into any episode yet.
She doesn't ever appear to take her glasses off for any reason, not even when she's getting treatments at a spa, including facial masks ("Hail Doofania!")
She appears to have the same personality as Linda, though perhaps a little more sarcastic. Interestingly Linda also at one point dated Doofenshmirtz. ("What Do It Do?")
Charlene shares another aspect with Linda: a daughter that wants to "bust" another person. In this case, it is Vanessa who wants to "bust" her father. ("I Scream, You Scream", "Hail Doofania!")
Though she and Heinz are divorced, she decided to keep the last name of "Doofenshmirtz" and attends Doofenshmirtz family reunions. ("Thaddeus and Thor")
She donates goods to charity, and encourages her daughter to do so. She also appears to be dating the man who drives the delivery van, Sam.("Finding Mary McGuffin")
She pays Heinz a rather hefty alimony, which he uses to help finance his schemes. ("Finding Mary McGuffin")
She is possibly the same age as Linda, as their daughters are in the same age group.