See Pope Francis changes to the annulment process here
Q. 1. When is the proper time to apply for an Annulment? Is it when a couple is separating, a year after having separated, during a divorce procedure or after a divorce has been granted? Any information would be greatly appreciated. Thanks.
A. 1. First of all, it should be understood that a person seeking an annulment is someone who has been married, is now divorced and (a) may or (b) may not wish to marry again. Reference of marrying again is a reference to a Sacramental Marriage in the catholic Church.
Before anyone can obtain an annulment, a divorce must have been granted by a civil court.
When applying for an annulment, you will need the following documents:
• Copies of the baptismal certificates of both Catholic parties involved.
• A copy of the civil marriage license.
• A copy of the church marriage certificate.
• A copy of the divorce decree certified or signed by the Judge.
If you are not divorced as of yet, you cannot apply for an annulment.