Dismissed Catalan President Carles Puigdemont and 13 officials from his government were scheduled to appear before the CNA on Thursday, while six members of the Catalan parliament went before the Spanish High Court.
The Catalan government was sacked last Saturday after they declared independence the previous day.
The Spanish prosecutor submitted a complaint against Puigdemont and his government for their push for secession.
Puigdemont remains in Brussels along with four of his former ministers. The Spanish prosecutor may now issue a European Union-wide warrant for his arrest.
Summoned Catalan leader Puigdemont remains in Belgium
"The climate is not good [in Madrid], it's better to keep a certain distance," Paul Bekaert, Puigdemont's lawyer in Belgium, told reporters on Thursday.
"If they ask, [Puigdemont] will cooperate with Spanish and Belgian authorities," the lawyer added.
It remains to be seen how Belgium will respond to the warrant. Many assume Puigdemont remains in Brussels to apply for political asylum, though he said in a press conference on Monday this was not his intention.
Belgian Prime Minister Charles Michel has reportedly "implored" his ministers not to speak on the issue of Catalonia.
Commentators have said that Puigdemont's choice to stay in Belgium may cause Spanish courts to hold the accused without bail.
The same was done to Jordi Cuixart and Jordi Sanchez, two pro-independence organisers held without bail on similar charges.
Jose Montilla, a Catalan politician from the Spanish Socialist Party (PSOE) and former president of the Catalan government, criticised Puigdemont and the four dismissed ministers who remained in Belgium: "Enough of the tricks that have led us here," he said.
Montilla told Catalan radio he hoped justice would be exercised with "prudence", but reminded the sacked government that "no one is above the law".
Centre-left PSOE has joined with the nationalist, centre-right ruling People's Party in their opposition to Catalan independence.
Catalonia's long push for independence
The accused former government is required to deposit 6.7m euros ($7.2m) with the courts. If they are unable to do so, their property will be seized.
The Catalan politicians could face up to 30 years in prison for the charges.
The Spanish High Court has given the accused members of parliament a week to prepare their defence and they are expected to appear before the court on November 9.
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