I have an App in iTunes Connect that has the status Pending developer release , i.e. it has been approved by Apple\'s review team and now I can release it m
No, you can only have one version of the app in the release process.
The only you can do is change the build of that version (Changing builds) while the version is not yet submitted for review. But, if the review has happened, you will need to reject the current binary, requiring the review to happen again.
Note that: