Water fountain objects are generally defined as evolved stars with low to intermediate initial mass accompanied by high-velocity molecular jets detectable in the 22.235 GHz H2O maser line. They are the key objects of understanding the morphological transitions of circumstellar envelopes during the post asymptotic giant branch phase. Masers are useful tools to trace the kinematic environments of the circumstellar envelopes. In this Letter we report the discovery of exceptionally uncommon excited-state hydroxyl (ex-OH) masers at 4660 and 6031 MHz toward the water fountain source IRAS 18460−0151. These are the brightest ex-OH masers discovered in late-type objects to date. To the best of our knowledge, prior to the current work, no evolved stellar object has been observed in the 4660 MHz ex-OH maser line. The ground-state hydroxyl (g-OH) masers at 1612 and 1665 MHz are also observed. The velocity components of the 4660 MHz ex-OH maser line and the much weaker 1665 MHz g-OH maser line all can be seen in the 1612 MHz g-OH maser line profile. The blueshifted components of the three masers are more intense than the redshifted ones in contrast to the ex-OH maser line at 6031 MHz. The relevance of the behaviors of the ex-OH masers to the circumstellar environments is unclear.