If his girlfriend is named, you are asking the Court for a divorce because your marriage has irretrievably broken downbecause of your husband's affair with his girlfriend. This means that your husband and his girlfriend will both receive a copy of the divorce petition from the Court, and must both return to the Court a form admitting to the affair.
If your husband admits to the affair, but his girlfriend does not, you cannot divorce him on the basis of his affair with her unless you can put forward additional evidence eg. She has had his baby.
This can often cause problems because whilst your husband may want to bring an end to your marriage, your husband's girlfriend may have nothing to gain in admitting to the affair.
Best practice is therefore not to name his girlfriend. It is usually considered only appropriate to do so if you want to ask for a Co-Respondent to pay a contribution towards your legal costs of the divorce proceedings.