"Ready to go"
European plans for a peacekeeping force to aid Ukraine once the war ends are now "mature" after months of planning, Keir Starmer said.
French president Emmanuel Macron meanwhile described the so-called coalition of the willing as "ready to go" once a ceasefire is agreed.
Planning for the coalition began in March following a summit at Lancaster House in central London, with the aim of policing a future end to the war in Ukraine.
That summit saw European allies rally to the Ukrainian cause, following Volodymyr Zelensky's tumultuous visit to the White House at the end of February.
Under the coalition plans, troops from France and the UK would be placed in Ukraine, while other countries would provide logistical support, all with the aim of deterring further Russian aggression.
European leaders have insisted the arrangement would be dependent upon an American "security guarantee", likely in the form of air support, something Donald Trump has been unwilling to openly say he would provide.
Mr Starmer and Mr Macron dialled into a call with allies who make up the coalition from the UK's military headquarters at Northwood in north-west London, where they made the announcement that preparations for the force are complete.
Speaking during the call on the last day of Mr Macron's state visit to the UK, the Prime Minister said: "I am very pleased to say today that these plans are mature and we are putting them on a long-term footing."