In this study, we used high-pressure infrared spectroscopy to probe the local structures formed between the ionic liquid [BMI][PF6] and the triblock PEO-PPO-PEO copolymer P123. The signals for the imidazolium C-H units of [BMI][PF6] underwent anomalous frequency shifts upon dilution, induced by order-to-order transitions. Appreciable changes in the relative band intensities of the signals for the imidazolium moieties occurred upon compression. Upon increasing the pressure, the ether C-O-C stretching band underwent dramatic changes, with a shoulder peak appearing near 1097 cm(-1) with relatively increasing intensity. It appears that high pressures somehow stabilize the hydrogen bonds formed between [BMI] and P123, possibly forcing the P123 molecules to dissociate the clusters of ionic liquid through enhanced hydrogen bonding with the imidazolium C-H units. Analogous to temperature-dependent behavior, we suggest the possibility of pressure-induced association of P123 molecules through elevation of pressure.