A terminal block structure and an unbuckling unit thereof are disclosed. The unbuckling unit has a base member and a rotary member, the rotary member is connected to the base member to be operated. The rotary member includes a first arm part, a second arm part extended from the first arm part and a rotary part disposed between the first arm part and the second arm part. The second arm part has a buckling unit, and the rotary part is connected to the base member. When the first arm part is applied with an external force, the rotary member rotates about the rotary part as a rotation center to drive the second arm part to ascend. Accordingly, advantages of easily to be pressed and operated, simple in structure and convenient to be assembled are provided.