While on the phone from Queensland today, Mrs Peach said her husband had been an excellent father to their two children.
"I really support Rod in this. I know it probably sounds really strange, but I do because he is really a good man. I know it's wrong in the eyes of the law, but there are deeper issues involved.''
They lived in New Zealand during their marriage and have two adult children, who are now both based in Australia.
Mrs Peach didn't know when or why her husband remarried, but said the union must have happened after the pair separated early last year.
"It's totally out of character for him. He is a really good man, he's been a really good father to the children, it's totally out of character. It's wrong, he is a good man. It's very, very, very strange.''
While she still hasn't spoken to her husband since news of the second marriage emerged, she said divorce was definite: "We will be divorced, yes.''
"I will have to contact him at some stage I suppose, but I'll wait for him to contact me.''
When previously asked if the allegations fitted her husband's character, Mrs Peach said: "I would have said no, but maybe I didn't know him at all.''
Court documents show Peach was a property developer and was originally from South Africa, but Mrs Peach said that contradicted what she thought he did for a job.
A tearful Sascha-Maria, one of Peach's two children, said she was devastated at the possibility of her father going to prison.
The crime is punishable by up to seven years in jail, or up to two years if both parties knew the marriage would be void because of a previous marriage.
The 19-year-old self-described `daddy's girl' worried he would be imprisoned for the charges, and might miss her wedding if she and her boyfriend decided to marry during that time.
"I hope that the judge is lenient. Seven years is too long for me to wait for him to get out, to walk me down the aisle,'' she said.
While still shocked about the charges, she defended her dad, saying he was a good man with high morals.
"He taught me it's not right to cheat. He said if you don't like someone, don't go out with them.''
The teenager is based in Queensland, but plans to fly back to New Zealand in March so her boyfriend and father can bond.
The details of the offending were not discussed in the courtroom today; only the guilty pleas were entered and a sentencing date set.
Peach and his lawyer declined to comment outside court today.
