Conformational preferences of a binary hydrogen-bonded complex between p-fluorophenol (pFP) and 2,5-dihydrofuran (DHF) have been studied by means of laser induced fluorescence (LIF) spectroscopy in a supersonic jet expansion. Calculation predicts two major conformers for this complex, one having a nearly linear geometry in which the two molecular moieties are bound only by an O-H center dot center dot center dot O H-bond, but in the other an additional C-H-H type interaction between an ortho C-H group of pFP and ethylene group of DHF contributes to the binding stabilization and results in a folded geometry for the complex with respect to a global view, although the H-bond angle of the latter is relatively larger. This prediction is realized experimentally by identifying transitions corresponding to the two discrete conformers in a vibrationally resolved LIF excitation spectrum of the complex, and the red shifts of Si-Si, origin band of pFP moiety of the two conformers are 542 and 659 cm(-1), respectively. The assignments are corroborated by means of dispersed fluorescence (DF) spectroscopy. In comparison, the LIF spectral bands for the pFP-tetrahydrofuran complex can be corresponded to only one conformer, whose S-1-S-0 origin transition shows a red shift (563 cm(-1)) somewhat similar to the linear conformer of pFP-DHF complex. Such similarities in spectral shifting behavior is consistent with the predictions of electronic structure calculations. The DF spectra also reveal that the energy threshold and pathways of vibrational dynamics in Si of the two conformers show different behavior. Excitation to 6a(1) level of pFP moiety of the folded conformer displays signatures of restricted intramolecular vibrational energy redistribution (IVR), whereas the linear form displays the emission feature for dissipative IVR