The photophysical properties of a polymer of intrinsic microporosity, namely, PIM-1, were characterized by steady-state and time-resolved fluorescence for solutions of PIM-1 in dichloromethane (DCM) or for a membrane made of PIM-1 immersed in hexane to which a quencher was added. Quenching of PIM-1 by the proton-donor trifluoroacetic acid (TFA), electron-rich tributylamine (TBA), and electron poor nitromethane (CH3NO2) was investigated and compared to those of the structural unit of PIM-1, the model compound M-1. Only TBA and TFA appeared to quench PIM-1 effectively. The sensitivity of monomer M-1 to the nature of the solvent led us to investigate how addition of a quencher would affect the fluorescence of the polymer PIM-1. Solvent effects were observed for TFA only and were carefully characterized. In particular, it was determined that these solvent effects could be neglected for TFA concentrations smaller than 1.4 mM. Quenching of PIM-1 by TBA was diffusional in nature and occurred in a similar manner for M-1 and PIM-1 in DCM, suggesting that M-1 is locally excited in PIM-1. All M-1 units were accessible and quenched effectively by TBA for PIM-1 in DCM and the PIM-1 membrane in hexane. Quenching of PIM-1 in DCM and in the membrane was more complex, showing a combination of static, diffusive, and protective quenching. The fraction of accessible M-1 units to TFA (f(a)) was determined to be equal to 0.5 for PIM-1 in DCM or in the membrane. The TBA and TFA quenching experiments led to the conclusion that the same accessibility was obtained for the fluorescent constituting units of PIM-1 dissolved in DCM or in a membrane immersed in hexane, in agreement with the known high microporosity of this polymer.