Two excited-state intramolecular proton transfer (ESIPT) active benzimidazole derivatives (1 and 2) were synthesized by acid-catalyzed intramolecular cyclization. The steady-state fluorescence spectrum in THF revealed that ring-fused derivative 1 exhibits a dual emission, namely, the major emission was from the K* (keto) form (ESIPT emission) at 515 nm with a large Stokes shift of 11 100 cm-1 and the minor emission was from the E* (enol) form at below 400 nm. In contrast, the normal emission from the E* form was dominant and the fluorescence quantum yield was very low (Φ ∼ 0.002) for nonfused derivative 2. The time-resolved fluorescence spectroscopy of 1 suggested that ESIPT effectively occurs due to the restricted conformational transition to the S1-TICT state, and the averaged radiative and nonradiative decay rate constants were estimated as ⟨kf⟩ = 0.15 ns-1 and ⟨knr⟩ = 0.60 ns-1, respectively. The fluorescence emission of 1 was influenced by the measurement conditions, such as solvent polarity and basicity, as well as the presence of Lewis base. The ESIPT process and solvatochromic behavior were nicely reproduced by the DFT/TDDFT calculation using the PCM model. In the single-crystal fluorescent spectra, the ESIPT emissions were exclusively observed for both fused and nonfused compounds as a result of hydrogen-bonding interactions.