The aim is to tackle online abuse and misleading content as well as making for a more positive atmosphere online, according to a press release.
Social media has "many joys" but also "a number of downsides," said the church. The guidelines include calls to "treat others how you would wish to be treated" and "think before you post."
The Archbishop of Canterbury, Justin Welby, unveiled the guidelines at Facebook's UK headquarters on Monday.
"Social media has transformed the way we live our lives. As Christians we are called to engage in a way which is shaped by the example of Jesus," Welby said in a press release.
"Each time we interact online we have the opportunity either to add to currents of cynicism and abuse or to choose instead to share light and grace."
The guidelines will apply to public responses to social media accounts run by the Church of England, the Archbishop of Canterbury and the Archbishop of York.
Inappropriate posts may be deleted or reported, or users blocked, the church said.
Welby also unveiled a voluntary digital charter centered on "truth, kindness, welcome, inspiration and togetherness," which individuals are encouraged to use to consider how their online interactions affect others.
People of all faiths and none are invited to sign up.
"We are saying that the church wishes to be present in the digital sphere, and the same force for social cohesion which it strives to be in the real world, and we want to work alongside social media companies in their work to make social media a safe and enlightening space for all," said John Sentamu, the Archbishop of York.
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