Prime Minister Tony Abbott on Wednesday announced that Australia would accept 12,000 Syrians from persecuted minorities.
That is on top of the 13,750 overall intake of confirmed refugees for 2015.
Australia will also expand its role fighting the so-called Islamic State (IS) to include its Syrian strongholds.
The Australian air force has been bombing IS targets in Iraq for about 12 months, but the US last month asked Australia to help pursue targets in Syria.
Mr Abbott's announcement is a major policy change. Several days ago he said Australia would take more Syrian refugees, but only as part of existing quota.
Europe is struggling to cope with its worst migrant crisis since World War Two, with tens of thousands crossing European borders.
The European Commission is due to announce plans to distribute 120,000 asylum seekers among EU member countries, with binding quotas.
