Both positions are due to come into force once the Lisbon Treaty has been ratified by all 27 EU members, with the decisions taken by a vote of all member states.
The Czech Republic is the only EU nation yet to have ratified the treaty but its president says it is getting closer to doing so.
The treaty incorporates the Charter of Fundamental Rights, which covers a wide range of EU citizens’ rights and will become legally binding once Lisbon enters into force.
Mr Miliband told the BBC’s Andrew Marr show that the positions could be filled “relatively swiftly” once the Czech Republic had approved the Treaty.
But he ruled himself out from being considered for either job.
“I am not a candidate for that. I am not available,” he said, adding that he was “committed” to his current job.
Endorsing Mr Blair for the role of EU president, he said whoever took the role needed to be on par with other world leaders and be able to “stop the traffic in Beijing and Moscow”.
“I think it would be good for Britain and for Europe if Tony Blair was a candidate and was chosen,” he said.
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