The European Union urged Russia to reverse what it called a clear violation of the Ukrainian border.
Stock markets slip as Russian convoy enters Ukraine But a senior security chief said Ukrainian forces would not attack the trucks, and had allowed them in, even without proper clearance, to avoid "provocations".
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Kiev called on international allies to unite in "a decisive condemnation of illegal and aggressive actions" by Russia.
Poroshenko said more than 100 trucks had crossed the border, of which only some had been checked earlier by Ukrainian officials inside Russian territory.
Other Ukrainian officials said only 34 or 35 of them had been properly checked.
Repeating earlier suspicions by Kiev that the aid cargo could be somehow used to support the separatists, the foreign ministry said: "Neither the Ukrainian side nor the International Committee of the Red Cross knows the content of the trucks. We are Slavs, we are together," Denikin told Reuters Television.
The Ukraine conflict has driven relations between Moscow and the West to their lowest level since the Cold War, with Western states imposing economic sanctions on Moscow and the Kremlin retaliating.
NATO has deployed extra troops in member states bordering Russia, including the Baltic states and Poland.
German Chancellor Angela Merkel is scheduled to visit Kiev on Saturday to show her support for Poroshenko - but diplomats say she is also bearing a message that he should consider calling a ceasefire so as not to incur a backlash from Putin.