Russia's decision to send more than 100 aid lorries into war-torn eastern Ukraine without permission has been widely condemned in the West.
The European Union and the US called for them to be withdrawn as it was a violation of Ukraine's sovereignty, and Nato said it would deepen the crisis.
But Russia said further delays were unacceptable - and also denied its troops and artillery were in Ukraine.
The first trucks have reached the besieged rebel-held city of Luhansk.
The UN is to hold an emergency meeting to discuss the convoy's entry, which Ukraine has described as an 'invasion'.
Nato chief Anders Fogh Rasmussen said in a statement that the developments were 'even more worrying as they coincide with a major escalation in Russian military involvement in eastern Ukraine since mid-August, including the use of Russian forces'.
Analysis: Jonathan Marcus, BBC defence and diplomatic correspondent
Nato's condemnation of the entry of Russia's aid convoy into Ukraine marks a significant hardening of its tone. The statement speaks of 'a major escalation in Russian military involvement in eastern Ukraine since mid-August, including the use of Russian forces'.
Indeed Nato goes further insisting that Russian artillery is being used against Ukrainian forces, with the fire coming both from across the border in Russia, and from within Ukraine itself. Western military sources speak of 'substantial' Russian military deployments inside Ukraine with battalion-size elements on the ground.
All this, taken with what Nato describes as the transfer of 'large quantities of advanced weapons' to separatist groups in eastern Ukraine, suggests a concerted effort by Moscow to prop up the defences of Luhansk and Donetz. Russia has consistently denied such charges but Russian armour has been seen crossing into Ukraine and marshalled near the border.
Ahead of the UN Security Council meeting, Russia's UN ambassador Vitaly Churkin said they had lost patience with Ukraine's chain of command and that Russia had had to act to save perishable goods.
'We regret if some Ukrainian officials are trying to stir the situation and create some political crisis, which is there but not for the reason of the Russian humanitarian convoy moving to the people in need,' he said
Mr Churkin also rebuffed Nato's accusations of military support for the Ukrainian separatist forces, saying the body had no proof.
His Ukrainian counterpart at the UN, Oleksandr Pavlichenko, said border guards had begun inspecting of some of the lorries on Thursday afternoon, but the Russians had decided to go ahead without waiting for them all to be cleared.
Foreign journalists were allowed to look into the Russian lorries earlier this week, and found they contained humanitarian supplies such as baby food and cereals.
Reporters at the scene saw rebel fighters in front of the convoy as it crossed the border near the town of Kamensk-Shakhtinsky.
Four months of fighting in eastern Ukraine have left more than 2,000 people dead and caused more than 330,000 people to flee their homes.
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