Starmer said it was clear the Russian president was "willing to gamble on global food security" after several grain ships en route to developing countries were damaged by Russian strikes.
Military intelligence published by the UK government overnight concluded that Russia had increased its attacks on Ukrainian port infrastructure in the Black Sea.
Between 5 and 14 October at least four merchant vessels were struck by Russian munitions, according to the intelligence assessment.
The strikes are believed to have delayed a vessel carrying vegetable oil destined for the World Food Programme in Palestine.
Ships loaded with grain destined for Egypt, two vessels carrying corn and WFP shipments bound for southern Africa were also affected, in some cases as collateral damage in strikes on port infrastructure.
"Russia's indiscriminate strikes on ports in the Black Sea underscore that Putin is willing to gamble on global food security in his attempts to force Ukraine into submission," the prime minister said in a statement.
"In doing so, he is harming millions of vulnerable people across Africa, Asia and the Middle East, to try and gain the upper hand in his barbaric war."
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