"There is no mediation possible between democratic law and disobedience, illegality," he told parliament.
Catalonia's separatist leaders yesterday signed an independence declaration but said they were suspending it in the hope Madrid would negotiate.
Rajoy also dismissed Catalan leader Carles Puigdemont's independence plan as a "fairy tale".
"It is not peaceful, it is not free, it will not be recognised by Europe and now everyone knows it will have costs," he added.
He was referring to several big companies which have moved their headquarters outside of Catalonia in recent days.
Also Read
Earlier today he proposed during an interview with CNN that a mediator be named to settle the crisis.
"Maybe, it could help (us) to talk if two people representing the Spanish government and two people representing the Catalan government just simply agree on one thing, for instance, naming a mediator," he said.
Puigdemont announced in the regional parliament yesterday that he had accepted the mandate for "Catalonia to become an independent state" following the contested referendum.
Disclaimer: No Business Standard Journalist was involved in creation of this content