The new law came less than a week after a shooting at an eastern Idaho middle school injured two students and a custodian.
The Republican governor signed the measure Monday. It passed the Idaho House and Senate with veto-proof majorities and carried an emergency notice, meaning it went into effect with Little's signature.
The new law is retroactive to Jan. 20, the day Biden was sworn in as president. It prevents all Idaho government entities from enforcing executive orders, federal laws, treaties, agency orders and rules of the U.S. government involving firearms, firearm components and accessories, or ammunition that conflict with the Idaho Constitution.
The signing followed Thursday's shooting in Rigby, where police have said a sixth-grade girl pulled a handgun from her backpack and fired multiple rounds inside and outside Rigby Middle School, about 95 miles (145 kilometers) southwest of Yellowstone National Park.
All three victims were shot in the extremities and none had life-threatening injuries, authorities have said. The girl was disarmed by a teacher.
Idaho already has a law passed in 2014 stating that the state's government cannot enforce federal actions that infringe upon Second Amendment rights.
Biden’s orders include a move to crack down on “ghost guns” — homemade firearms put together from purchased gun parts that lack serial numbers to trace them and are often acquired without background checks.
Biden also moved to tighten regulations on pistol-stabilizing braces like the one used in the Boulder, Colorado, supermarket shooting last month that left 10 dead, including a police officer. The braces for handguns allow them to be fired from a shoulder, like a rifle.
Biden is also seeking so-called “red flag laws” allowing family members or law enforcement to seek court orders that temporarily bar people in crisis from accessing firearms if they pose a danger to themselves or others.
Backers of the legislation signed by Little also said it prevents Idaho gun and ammunition manufacturers from being held responsible if their products are used in crimes.
Opponents said creating legislation that conflicts with federal laws could mean the state will lose federal funding. Backers have acknowledged that possibility but said Idaho lost no federal funding after the 2014 law was approved.
Biden has said his priorities for Congress include passing the Violence Against Women Act that would prohibit people previously convicted of misdemeanor stalking from possessing firearms; eliminating lawsuit exemptions for gun manufacturers; and banning assault weapons and high-capacity magazines. He’s also called on the Senate to take up House-passed measures to close loopholes in background checks for gun purchases.
But with an evenly divided Senate and any gun control legislation requiring 60 votes to pass, Democrats would have to keep every member of their narrow majority while somehow getting votes from 10 Republicans.