Rio paid A$16.5 per share, valuing the deal at A$1.06bn ($1.1bn; ?700m).
However, it was forced to raise its offer and extend deadlines due to a slow response from the shareholders.
The move came after it acquired Brazilian steelmaker Companhia Siderurgica Nacional's 19.35% holding in Riversdale earlier this year.
Rio said it will now move to a compulsory acquisition of the company.
"This is a great outcome for Rio Tinto," said Doug Ritchie, Rio Tinto Energy's chief executive.
"The Riversdale acquisition reinforces our strategy of investing in and operating, long-life, cost-competitive mines and businesses with significant growth potential," he added.
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