In order to develop organic semiconductor materials with good performance, herein, a series of naphthalene derivatives were designed and synthesized by a “building-blocks approach” connected through α-bond, double bond, and triple bond, respectively. Thin-film transistors were fabricated in single-component and two-component modes based on these naphthalene derivatives by combining the F₁₆CuPc as the n-type material. The ambipolar performance was investigated by adjusting the device preparation procedure with the hole and electron mobility of up to 10⁻² cm² V⁻¹ s⁻¹. Furthermore, the electrical performance was also improved to 0.73 cm² V⁻¹ s⁻¹ using the two-component bilayer configuration.