Among different hydrogen bonds, the O-H…O and N-H…O bonds most often occur in liquid phase. It plays a crucial role in biological systems such as proteins and DNA base pairs and is essential for life processes. In all hydrogen bonded molecules there is a strong possibility of solute and solvent interaction. An effort to explain the ground and excited state intra/intermolecular charge transfer photophysics of Pyrrole-2-Carboxyldehyde (PCL), Pyrrole-2-carboxylic acid (PCA) and its related compounds in UV-VIS and IR region has been reported here.Quantum chemical calculations indicate that PCA, PCL are good candidate for intramolecular proton transfer in excited state. The absorption spectra of PCA in different solvent point the presence of intramolecularly hydrogen bonded closed conformer in the form of 280 nm band. Stokes shifted fluorescence of PCA at 310 nm in hydrocarbon solvent and hydroxylic solvents have been identified to be due to normal molecule. Variation of pH results enhancement or decrease of emission from ionic conformer with parallel dwindling of emission of neutral species. Possibility of intramolecular and intermolecular hydrogen bonding of PCL in ground state was established theoretically by the distance N5-H6………O11 of acidic and basic moieties of PCL and experimentally it is verified by the IR stretching and bending mode vibrations of different parts of the molecule. The possibility of transfer of hydrogen from pyrrole ring towards formyl ring in excited state indicates in the light of difference in bond length and bond angle, dipole moment, enthalpy, Gibbs free energy etc.