The 24-year-old attacking midfielder, who joined from Hartlepool on a two-year deal last week, was a man in demand after scoring 12 goals in all competitions last season.
“At one point I was linked with a lot of teams,” said Sunderland academy graduate Molyneux.
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"They were two clubs I was really looking at and seeing what could happen, but things didn’t work out. Both teams, especially MK Dons, said they wanted to look at the loan market first.
"I said ‘I can’t wait around’. I wanted to get back in for pre-season, so that one broke down. Bristol wanted to sign someone else and that obviously fell through.
"There was quite a lot of teams in League Two that were interested but Doncaster was the standout one for me.”
Rovers boss Gary McSheffrey confirmed Molyneux was a top target of his this summer, having watched him since March.
He said: “He was a standout player last year in the division, one of the best attackers who scored some great goals, real eye-catching goals.
“We want him to come here and do the same.”
But the player resisted the club’s initial approach via Graeme Lee, who played for Rovers and managed Molyneux at Hartlepool last term.
"I was linked with a lot of teams in League One and the Championship, so I wanted to explore that first,” Molyneux said.
"When the option came back around to meet up with the gaffer I spoke with Jonny Mitchell, who was already here. He had a lot of good things to say.
"Then I spoke with previous players [...] Danny Amos and Omar Bogle, who was here last season. There were a lot of positive talks and I think that was the main thing for me.
Molyneux could make his first Doncaster appearance against Armthorpe Welfare on Saturday.