Europe is faced with an unprecedented wave of migrants fleeing conflict and poverty in north Africa and the Middle East, many of them crossing the Mediterranean on flimsy fishing boats.
Speaking in Menton, near the Italian border, on Saturday, Valls said the introduction of quotas for migrants has never been in keeping with French proposals.
France joins Britain, Hungary, Poland and several other member states in opposing the EU plan.
Valls said only genuine asylum-seekers fleeing repressive regimes should be allowed to stay in Europe and other migrants should be expelled.
Nearly 1,000 migrants and dozens of smugglers were intercepted in the Menton area this week.
France is instead calling for a European system of border guards and more preventative measures in the migrants' countries of origin.
One such initiative is the creation of a migrant reception centre in Niger, due to open at the end of the year in Agadez.
Interior Minister Bernard Cazeneuve announced the plan on Friday with the support of Niger's president Mahamadou Issoufou.
Niger is a key transit country for migrants hoping to reach Libya where smugglers to cross the Mediterranean.
Meanwhile, the European Union this week also firmed up plans to crack down on people smugglers.
On Thursday Germany said it was confident of winning UN Security Council approval for an ambitious EU naval military operation, part of a wider plan to stem the flow of migrants coming from the shores of North Africa.
In an effort to destroy the human traffickers' "business model", the EU wants to be able to identify, intercept and possibly destroy the smugglers' boats in Libyan waters, something that would require a United Nations resolution.