However, their romance became short-lived when Milojko claimed to have caught Milijana kissing fellow contestant, 60-year-old Nemanja Stamatovic Zabac.
Milojko called it quits after he caught the pair in the shower together, theDaily Mirror reports.
Milojko reportedly suffered from high levels of stress over the alleged cheating scandal and was rushed to hospital.
Not long after, he requested help from a lawyer to begin divorce proceedings.
A producer from the show told reporters: "He had a hard time having to divorce Milijana, which is why as a production team we had to react.
"We took him out of the villa during the day and took him to a hospital.
"He was immediately given medical help, and it was revealed that he was under high pressure due to the stress he had experienced on the reality show."
Following his recovery, Milojko befriended a fellow contestant from the show, Aleksandra Jaksi, who asked if he and his young wife had been faithful in their marriage.
"You know how old I am?" a heartbroken Milojko said. "We didn't have a deal. I was looking for a lawyer to have a nice divorce."
According to the publication, Milijana's new lover is pressing her to share the $55,000 she is allegedly going to receive from the divorce.
The Serbian couple made headlines back in March this year when Milijana revealed Milojko didn't need Viagra.
At the time, Milijana said they had sex "almost every day".
"I don't see what is strange with that. But since Mikan had his heart operation, I have to go easy on him in bed," she said.
In December last year, the 74-year-old underwent heart surgery and, despite their 53-year-age gap, continued to go ahead with their wedding plans.
Milijana said Milojko was like a "young man when it comes to sex".
"He doesn't need Viagra. Although, I don't know much about younger men, as I've always been with men older than me," she said.
Milijana admitted she didn't like young guys.
"I've liked older men since forever," the 21-year-old said in the March interview.
Milojko has three children from his first marriage – aged 40, 35 and 30 – and two grandchildren, aged 13 and 11.