Ukraine has accepted proposals for a ceasefire and a summit meeting, but so far Moscow has been noncommittal.
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There is "absolutely no evidence" that Russia's President Vladimir Putin wants to negotiate an end to the full-scale invasion of Ukraine, the head of the UK's foreign intelligence agency said on Friday.
Richard Moore, chief of MI6, said Putin was "stringing us along."
"He seeks to impose his imperial will by all means at his disposal. But he cannot succeed," Moore said.
"Bluntly, Putin has bitten off more than he can chew. He thought he was going to win an easy victory. But he – and many others – underestimated the Ukrainians."
The war has continued unabated in more than three years since Russia went on a full-scale invasion of its neighbour in early 2022, despite renewed US-led efforts in recent months to steer Moscow and Kyiv to a settlement.
Ukraine has accepted proposals for a ceasefire and a summit meeting, but Moscow has been noncommittal.
US President Donald Trump said during a state visit to the United Kingdom on Thursday that Putin "has really let me down" in peace efforts.
Moore was speaking at the British consulate in Istanbul after five years as head of MI6. He leaves the post at the end of September, when the agency will get its first female chief, Blaise Metreweli.
During his tenure, Russia launched its full-scale invasion of Ukraine, a war that still rages, as Moscow continues to pound Ukrainian cities with daily missile and drone attacks.
Moore said the all-out invasion had strengthened Ukrainian national identity and accelerated its westward trajectory, as well as pushing Sweden and Finland to join NATO.
"Putin has sought to convince the world that Russian victory is inevitable. But he lies. He lies to the world. He lies to his people. Perhaps he even lies to himself," Moore said at a news conference.
'Pavlov's tinkling bell inside the Kremlin'
Referring to the Russian scientist Ivan Pavlov, who conditioned dogs to respond to a bell, Moore said a phone call from the Russian president was "the equivalent of Pavlov's tinkling bell inside the Kremlin, eliciting learned behaviour to tell Putin whatever it is the system thinks he want to hear."
He said that Putin was "mortgaging his country's future for his own personal legacy and a distorted version of history" and the war was "accelerating this decline."
Moore, who previously served as the UK's ambassador to Turkey, added that "greater powers than Russia have failed to subjugate weaker powers than Ukraine."
Analysts say Putin believes he can outlast the political commitment of Ukraine's Western partners and win a protracted war of attrition by wearing down Ukraine's smaller army with sheer weight of numbers.
Ukraine, meanwhile, is racing to expand its defence cooperation with other countries and secure billions of dollars of investment in its domestic weapons industry.
The spy chief was speaking as MI6 unveiled a dark web portal to allow potential intelligence providers to contact the service.
Dubbed Silent Courier, the secure messaging platform aims to recruit new spies.
"To those men and women in Russia who have truths to share and the courage to share them, I invite you to contact MI6," Moore said.
Not just Russians but "anyone, anywhere in the world" would be able to use the portal to offer sensitive information on terrorism or "hostile intelligence activity," he said.