But what Luke didn't know was that before his bride even got to their big day, she was having second thoughts.
"I just keep thinking to myself, what the f--k are you doing?" she revealed as she was prepping for the event.
"This is the most petrified I've ever been in my life," she added, admitting that she'd been crying non-stop after saying goodbye to her two-year-old twins.
"It's only been one day and I'm already really upset about it," she confessed – leaving us wondering just how she'll cope being away from the tots for several weeks.
Despite her panic, the 38-year-old made it to her Blue Mountains nuptials, exchanging some sweet vows with Luke – a father of two himself, to two teenage girls.
"I think there is a spark there," he quipped after the ceremony, which seemed to go off without a hitch.
But it wasn't long after the rings were on that Poppy began to feel "overwhelmed" again, and threatened to quit the show, leaving poor Luke dumbstruck.
"Initially, I was okay... He's really nice, a nice genuine person. We clicked," she shared, fighting back tears.
"But I'm not over the fact that I left my kids to do this."
"I feel guilty... I don't know if I can do it."
Poppy's concerns only grew stronger as the newlyweds set off to take photos, with the star admitting she knows this is going to be a constant struggle for her throughout the series.
But can she overcome it for the chance at finding true love?
(Meanwhile, poor Luke – he was trying so hard to be supportive and she couldn't even make eye contact!)
Things didn't get much better at the reception, where Poppy made the shocking admission that she wanted to go home – leaving Luke wondering if his search for love was over before it started.
"I don't know how to take it," he revealed, despite understanding how difficult the situation is for the mum of two young kids.
"It's really hard to be positive. I know she doesn't mean to but it's pretty hurtful. This is a train wreck."
Luckily, Poppy's best friends were able to get through to the 38-year-old, who was clearly totally overwhelmed by the whole situation – and gave her the courage to open up, put her fears aside and "give him a good go".
But despite getting their romance back on track, could this spell disaster for this couple before they've even begun?
The story of how Poppy became a single mother is a shocker.
Now living in Wollongong with her boys, Poppy discussed the moment she found out her hubby was cheating.
"This thing just went off in my head and I'm like, 'You've got his email password.' I logged into the email right then and there and there it was, photos of them two together.
"It still upsets me to talk about it, just because [of] my boys."