Ambipolar semiconducting materials offer great potentials in complementary-like organic logic circuits. Accessing such logic circuits demands balanced hole and electron mobilities. However, the lack of ambipolar high-mobility polymer semiconductors with balanced charge carrier transporting properties precludes the rapid development of organic logic circuits. In this context, structural modification of semiconductor materials to enhance the electron/hole transport is of great urgency. Herein, a multi-functionalization strategy is used to achieve this goal. Combined electron-withdrawing moieties involving fluorine and pyridinic nitrogen atoms can not only reduce the frontier molecular orbital energies but also planarize the polymer backbone, demonstrating synergetic effects on the control over carrier injection process at the metal-semiconductor interface and microstructure-sensitive charge transport in the channel. A balanced ambipolar behavior with electron/hole mobilities of 3.88/3.44 cm^2 V^-1 s^-1 was observed, and complementary-like inverters with high gains of greater than 200 were achieved. Microstructure and thin-film morphology was characterized to further reveal the relationship between device performances and macroscopic observables. This multi-functionalization strategy bodes well for developing new ambipolar semiconducting materials.