Room-temperature ionic liquids, particularly those based on substituted imidazolium cations, are currently being extensively studied for a variety of applications. Herein, we explore the suitability of several imidazolium salts in optical applications by carefully examining the electronic absorption and fluorescence behavior of these substances, generally believed to be transparent in most of the UV region and fully transparent in the visible region. It is shown that all imidazolium ionic liquids are characterized by significant absorption in the entire UV region and a long absorption tail that extends into the visible region. These absorption characteristics are attributed to the imidazolium moiety and its various associated structures. When excited in the UV or early part of the visible region, these liquids exhibit fluorescence, which covers a large part of the visible region and shows dramatic excitation wavelength dependence. The excitation wavelength dependent shift of the fluorescence maximum has been rationalized taking, into consideration the existence of the various associated structures of the ionic liquids and the inefficiency of the excitation energy-transfer process between them. The results imply that these liquids may have serious drawbacks in some of the optical studies.