Yes, velocity and acceleration can act in opposite directions. Take the example of motion under gravity, where the object moves in the upward direction. In this case, velocity is in the upward direction, but the acceleration due to gravity is in the downward direction. Thus, the acceleration and velocity of the object are in opposite directions.Simple Harmonic motion also exhibits the same phenomenon.
Also velocity and acceleration can act perpendicular to each other, as in the case of circular motion.
Thus acceleration and velocity can act in different directions.