The couple – who share three daughters and have been married since 2012 – took to social media on Saturday (26 February).
The actors encouraged fans to make donations to assist Ukrainians who have been displaced by the ongoing invasion.
On Thursday (24 February), Russia launched a full-scale attack on its neighbour. Heavy fighting is underway in Ukraine’s second city as Russian troops entered Kharkiv in the early hours of Sunday morning (27 February).
Reynolds, 45, wrote on Twitter: “In 48 hours, countless Ukrainians were forced to flee their homes to neighbouring countries. They need protection.
“When you donate we’ll match it up to $1,000,000, creating double the support.”
The Deadpool star shared a link to the UN Refugee Agency (UNHCR) where people can donate money to help displaced families.
Lively, 34, took to Instagram to post a similar message, writing: “@VancityReynolds [Reynolds’ Instagram handle] and I are doubling every dollar donated to @usaforunhcr up to $1,000,000. Link in bio to donate.”
She continued: “@Usaforunhcr is on the ground helping the 50,000+ Ukrainians who had to flee their homes in less than 48 hours.
“@Usaforunhcr is providing life saving aid, and also working with neighbouring countries to ensure protection for these families.”
The Gossip Girl star wrote the caption alongside an image taken from the UNHCR of a child being lifted into someone’s arms.
Major attacks in Ukraine on Saturday night (26 February) included a gas pipeline outside Kharkiv that was set ablaze by Russian troops, and an oil depot in Vasylkiv near Kyiv that was destroyed by a Russian missile strike.
You can follow along with updates at The Independent’s Russia-Ukraine liveblog here.