Mr Molesi is Samoan and Mr Brobbel is Canadian-Dutch, making this one of the first Pasifika same-sex weddings.
After the ceremony, the couple said they felt great after finally being able to tie the knot.
Sydney friends Jacynta Olano and Ana Newton said the couple had decided to have the ceremony in Masterton after New Zealand made the law change.
"This is what they were wanting for a long time," said Miss Olano.
Miss Newton said she couldn't understand why Australia hadn't legalised same-sex marriage yet, especially as Sydney Mardi Gras was one of the country's most popular events.
"I don't think it should be illegal in Australia."
Miss Olano said Ralph did a lot for the gay community in Sydney.
She said when Australia's first Maori drag performer and anti-discrimination activist Carmen Rupe passed away, he organised a float dedicated to her at Sydney Mardi Gras.
Ralph's cousin Capri Leonardo Jackson, also born in Masterton and who now lives on the Gold Coast, said it was an historic moment for the town.
Miss Jackson said Ralph used to drive her around for drag queen competitions. "Back then it was really hush hush. In a small town, it's really hard, you're brought up to be butch, play rugby. You're not fitting in." She said the wedding was another positive step after transsexual Georgina Beyer became mayor of Carterton and the world's first openly transsexual member of Parliament. "It's another stepping stone to start awareness, especially in a small town."
Miss Jackson said the Australian Government was losing out with all the economic benefits of weddings coming to New Zealand.
"All the Kiwis are coming back here to get married."
Celebrant Carol Pilcher said it was the first same-sex marriage she's performed.
It was no different from any other wedding, it was all about love, she said.
"I don't think it's about whether they are the same sex or not."
About 1000 same-sex couples in Australia want to marry in New Zealand despite the marriages not being legally recognised in Australia, according to the Australian Marriage Equality lobby group.
Wairarapa is proving to be an attractive choice for same-sex weddings, as bookings are starting to come in.
Julie Riddell, a celebrant and South Wairarapa district councillor, said she had been booked for some same-sex marriages in the New Year.
"I'm very happy to do them," she said.
The owners of Lansdowne House said they had several inquiries from same-sex couples in Australia but nothing was confirmed as yet.
The Marriage (Definition of Marriage) Amendment Act, passed in August, enables couples to marry regardless of their gender or sexual orientation.
Since the law change, 82 same-sex couples have married in New Zealand.
Over 50 of the marriages were between New Zealanders.
New Zealand is the first Asia-Pacific country and 14th in the world to legalise gay marriage.
