The meeting came as protesters streamed into the capital from mainly western regions for a mass rally tomorrow, boosting thousands already camped out on Kiev's Independence Square, focal point of recent demonstrations.
Russia, meanwhile, yesterday pointedly demanded the European Union keep out of Ukrainian affairs.
Mr Yanukovich, yielding to calls from the international community, began round-table talks with the opposition to try to find a way out of the conflict which has put Ukraine at the centre of an East-West tug-of-war.
However, with the opposition insisting on core demands such as the dismissal of his government, the talks seemed unlikely to head off another outpouring of anger against him.
Boxing champion-turned-opposition politician Vitaly Klitschko said: "This round-table was simply a declaration and not a single step was made to meet the opposition. I have the impression the authorities did not listen to a single one of the demands of the opposition."
Despite talks in Brussels by his government aimed at securing financial aid from the EU for his near-bankrupt country, Mr Yanukovich still appeared on course to go to Moscow next week to tie up a trade agreement which the opposition fears could slam the door on integration with Europe.
Highlighting the high geo-political stakes, Russian Prime Minister Dmitry Medvedev said Ukraine must avoid a "tectonic split".
He said the appearance of EU politicians at Kiev protests was a "crude interference" in Ukraine's affairs - a clear reference to EU foreign policy chief Catherine Ashton and EU foreign ministers who have visited protest sites in recent weeks.
The crisis began last month when his government suddenly backed off a landmark trade-and-political agreement with the EU after years of preparation and announced it was reviving trade relations instead with former overseer Moscow.
Since then the capital has seen numerous, sometimes harshly handled, pro-Europe rallies, involving hundreds of thousands of people at the weekends, who accuse Mr Yanukovich of turning the clock back and selling out national interests to the Kremlin.
The opposition leaders indicated they would insist Mr Yanukovich meet their core demands which include the dismissal of the government and early elections.
Former economy minister Arseny Yatsenyuk said: "We will pass on to him (Yanukovich) your demands. We will fight for our common victory."
For his part, Mr Yanukovich sought to take a neutral stance in the conflict which has involved police heavy-handedness against peaceful protesters that has drawn condemnation from the international community.
He criticised police tactics and proposed an amnesty for those detained in the protests but he gave no indication he would sack Prime Minister Mykola Azarov as demanded by the opposition. Demonstrators have re-built barricades torn down by police.