The first time the Supreme Court declared any portion of a law to be unconstitutional was 1803, in the celebrated case of Marbury v. Madison. In this case, the Court established the principle that judges could declare a law void if it was found to be contrary to the Constitution. This power has come to be called judicial review.
The finding of Marbury, the first exercise of judicial review by the Supreme Court, was merely that one provision in the Judiciary Act that Congress had passed in 1789 was not warranted by the Constitution. In other words, judicial review was first used to keep the federal government within the bounds established by the Constitution. It was many decades before the Courts did use a provision from the Bill of Rights to strike down a congressional act. And the first case to do so was the Dred Scott decision of 1857, in which the Court held that outlawing slavery in the territories would deprive slaveholders of their property “without due process of law,” as required by the 5th Amendment. This was not an auspicious beginning for establishing the authority of the Supreme Court as the defender of individual rights.