In a speech on Tuesday Sir James Munby backed calls for a reform of marriage law by referring to a controversial case which has forced a woman to stay married to a man she wishes to divorce.
The case, Owens v Owens, is currently being considered by the Supreme Court, and was overseen by Sir James in the Court of Appeal last year.
Currently couples who wish to split must cite a reason that the marriage is unviable, such as unreasonable behaviour or adultery on the part of one party.
Mrs Owens was unable to divorce her husband because she could not prove that his behaviour had been sufficiently unreasonable.
Sir James told an audience at the Law School, University of Edinburgh, that he had been unable to grant Mrs Owens a divorce because while she, "with some justification, considered herself trapped in a loveless marriage, had failed to establish any ‘ground’ upon which she was entitled to a decree; specifically because, to use the convenient short-hand expression, she had failed to establish ‘unreasonable behaviour’ on the part of her husband."
The law is "very badly in need of reform", he said.
Sir James, in his judgment on the case in the Court of Appeal last year, said that "the law which the judges have to apply and the procedures which they have to follow are based on hypocrisy and lack of intellectual honesty".
The senior judge is the latest to back a change in the law. Last year Baroness Hale of Richmond, the President of the Supreme Court, also said blame should be removed from the divorce process.
Sir James also said the lack of legal recognition for cohabitees was "an injustice which has been recognised almost as long as I have been in the law".
He added: "How many more women are to be condemned to injustice while our masters delay, constantly persuading themselves, presumably, that the time is not yet ripe?"