Writing on her page on the social networking site, Glanville criticised the singer for her "inappropriate" behaviour after discovering that Rimes apparently planned to sing at hers and Cibrian's son Mason's elementary school.
“I told Eddie to please tell you that I think it is highly inappropriate for you to sing in my son's class on Friday," she wrote.
"Boundaries!! It's Mason's week to share his family with the class. It isn't ur place. (sic)"
Glanville added: "Let Eddie read a script. You are not his parent. Respect!"
X17 Online reports that Rimes did not respond to the tweets, instead asking followers to ignore such messages.
"I have asked once and would hope my fans would please respect my wishes…please do not retweet me anyone else's drama," she posted.
Glanville filed for divorce from Cibrian in August 2010 following his affair with Rimes.
Rimes and Cibrian announced their engagement in December 2010.