There is no such thing as "toning". To make the muscle stand out more or appear more "toned", body fat must be reduced. That is achieved through a combination of diet and exercise. It isn't possible to reduce fat in a particular area of the body, so you have to lose fat everywhere.
The largest muscle groups in the thigh are the quadriceps (the large muscle in the front of the thigh) and the hamstrings (in the back of the thigh). Any exercise that straightens the knee works the quads, and exercises that bend the knee or straighten the hips by pivoting your pelvis will work the hamstrings. Those exercises used as part of a diet and exercise program will increase the size and strength of those muscles.
Some exercises that work those muscles include squats, dead-lifts, lunges, leg extensions, leg presses, leg curls and variations of those exercises.