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No, they cannot legally work without a work permit.

Indeed, they need a work permit. (we had a lot of threads discussing this)

You can see different type of work permits here:

The other type B is when the employer sponsors a work permit for the hire.

Work permit A can be applied only after being employed in work permit A for at least 4 years.

Work permit C is for individuals meeting some special criteria (students, asylum seekers).

Correction on Work permit C:     (Flanders site)

There is a revised list of criteria. Approval is on case to case basis. it is the best to check this directly with the department of Economic Migration .

Another option is the professional card (self employed), for selected type of qualifications and skills:

Thank you for your replies. I am aware of the different kinds of work permits available here. I was of the opinion that once you have received the permanent residency card, your spouse would not require a work permit on the basis of your residency. Thank you for bursting the bubble  I guess it is only for Non EU spouses of the EU citizens who are allowed to work without work permit?

Permanent residence is after 5 years. Do you really mean this?

@schoolmum I know permanent residency is after 5 years. My question was about work permit requirement for spouse which has been answered by the two gentlemen.