It comes after campaigning from labour advocates across the world calling for such a law, citing studies that show employees are working longer hours and struggling to switch off from work, especially while based at home.
Currently the rule will only affect civil servants, but there are hopes that the rule can be rolled out to private sector employees.
However, unions are concerned that extending the law to all employees will be a challenge.
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President of the Belgian union FGTB-ABVV, Thierry Bodson, told
VICE World News: "This decision taken for public sector workers is very important [and] opens up a real right to disconnect for 65,000 federal civil servants.
"This is a step forward, but it cannot be automatically applied to other workers in Belgium. For workers in the private sector, several laws will have to be amended to allow this right to disconnect. Our union wants to extend this rule or principle to the private sector, but the legislative path will be longer and much more complex."
In recent years, Italy, France, Spain and Portugal have all introduced similar laws protecting workers’ rights to be unreachable by work.