For example, if a car is driving forward and the driver slams on the brakes, the velocity of the car will be positive and the acceleration will be negative. The car will slow down until it comes to a stop.
Another example is if a ball is thrown into the air. The velocity of the ball will be positive as it rises, but the acceleration will be negative due to gravity. The ball will eventually reach its peak height and then begin to fall. The velocity of the ball will be negative as it falls, but the acceleration will still be negative. The ball will eventually hit the ground.