Newly developed ultraviolet(UV)-infrared(IR) double resonant spectroscopy with relaxed fluorescence detection has been applied to the observation of the IR spectrum of aniline in the first electronic excited (S₁) state. In the 2900-3900 cm^-1 region above the origin of S₁, two types of IR transitions have been observed. One is the vibrational transition involving the NH₂ and CH stretching vibrations of aniline in the S₁ state. By examining the IR spectra for several deuterium substituted species, we found that the NH₂ stretching vibrations of S₁ locate at 3000 cm^-1, representing extremely large frequency decreases (500 cm^-1) upon the electronic excitation. The other is the anomalously broad transition appearing above 3300 cm^-1. The transition can not be assigned to any type of the vibrational transition of S₁ since it occurs in all the isotopomers examined, and we conclude it as the vibronic transition to a new electronic excited state, which may be called as the new “S₂” state. We examined the same energy region by measuring the one photon laser induced fluorescence (LIF) and two photon absorption spectra from the ground electronic (S₀) state, and we found an intense band origin of the new “S₂” state at 37104 cm-1 in the two-photon spectrum. From the consideration of the symmetry, the new “S₂” is thought to have B₁ symmetric species, which is in good agreement with the recent SAC-CI calculation reported by the Nakatsuji's group, and the new “S₂” state is assigned to the 3s-Rydberg(¹B₁) state.