A Pd(II)-catalyzed straightforward oxidative naphthylation of unmasked 2-pyridone derivatives is described using a twofold internal alkyne as a coupling partner. The reaction proceeds through N-H/C-H activation to provide polyarylated N-naphthyl 2-pyridones. An unusual oxidative annulation at the arene C-H bond of the diarylalkyne leads to the formation of polyarylated N-naphthyl 2-pyridones, where the 2-pyridone-attached phenyl ring of the naphthyl ring is polyaryl-substituted. Mechanistic studies and DFT calculations suggest a plausible mechanism based on N-H/C-H activation. The N-naphthyl 2-pyridone derivatives were studied to explore encouraging photophysical properties.