The five failed to attend a high court hearing in Madrid on Thursday when nine other ex-members of the regional government were taken into custody.
One of those detained has been freed on bail of €50,000 (£44,000; $58,000).
They all face charges of rebellion, sedition, and misuse of public funds for pursuing Catalan independence.
Puigdemont has said he will not return to Spain unless he receives guarantees of a fair trial.
Belgium will "study" the warrant, a spokesman for the state prosecutor told AFP news agency.
The regional parliament in Catalonia voted to proclaim an independent republic a week ago, following an illegal referendum on independence organised by the Catalan government on 1 October
No other country recognised the move and the Spanish central government moved swiftly to impose control, using emergency powers under the constitution.
The warrants were sent to Belgian prosecutors, who have 24 hours to decide whether the paperwork is correct.
If they do, they will forward them on to a judge who will decide whether Mr Puigdemont and the four others should be arrested.
With agency report
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