We have a project set up with a product backlog in Visual Studio Online.
However, I now find that in TFS TFVC has been configured as the source control provider rather than Git, which we will be using.
Does anyone know if it is possible to change from TFVC to Git without creating a new team project?
Currently No, but they are working on it, no release dates yet. See https://visualstudio.uservoice.com/forums/121579-visual-studio/suggestions/3612921-support-converting-tfs-online-project-from-tfsvc-t
Yes, in Visual Studio Online/Team Services since March 2016 and in TFS 2015 Update 1, it's possible to add a Git repo to a team project created with Team Foundation Version Control (TFVC).
To see both types of repos in Visual Studio you need VS 2015 Update 1 or higher.
You can find more details here.