The Shell petrol station and Geelong refinery owner came to an agreement to buy the On The Run convenience chain from South Australian Shahin family's Peregrine Corporation for $1.15 billion.
Under the deal, Viva will acquire OTR's 205 convenience stores, including 174 integrated fuel and convenience stores and 31 stand-alone stores.
OTR's 257 Smokemart and Giftbox tobacco and cigarette wholesale stores will also be transferred to Viva under the deal.
The acquisition will be "transformational" and will allow the petrol and diesel company to shift towards electric vehicles, Viva chief executive Scott Wyatt says.
"As our stores increasingly become retail destinations, we expect convenience earnings will grow and reduce our dependency on traditional fuels," he said.
"OTR outlets offer an attractive and welcoming store environment, supporting increased dwell time, which is likely to be a key factor in successfully introducing electric vehicle recharging facilities over time."
OTR Group founder Yasser Shahin will stay on following the acquisition to help run the business, saying the merger between the two companies has "enormous industrial logic".
Viva Energy stocks jumped as high as 5.8 per cent to reach $3.26 a share on the ASX 200 following the announcement.
Peregrine Group started from humble beginnings, established by the Shahin family from a small BP service station in South Australia in 1984.
The company has since grown to become one of the top 15 private firms in Australia and the largest private company in the state, generating more than $2 billion in annual revenue.
The transaction is set to be finalised in the second half of 2023 subject to approval by the competition regulators.
Viva acquired the network of Coles Express petrol stations from Coles Group for $300 million in September, with the brand set to be replaced by OTR once the acquisition is finalised.
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