ABSTRACTV532 Oph has been found to be a member of the rare, hydrogen-deficient R Coronae Borealis (RCB) stars from new photometric and spectroscopic data reported in this article. The light curve of V532 Oph shows the sudden, deep, irregularly spaced declines characteristic of RCB stars. Its optical spectrum is typical of a warm (Teff ∼ 7000 K) RCB star, showing weak or absent hydrogen lines, C2 Swan bands, and no evidence for 13C. In addition, the star shows small pulsations typical of an RCB star and an infrared excess due to circumstellar dust. It also appears to be significantly reddened by foreground dust. The distance to V532 Oph is estimated to be 5.5–8.7 kpc. These new data show that this star was misclassified as an eclipsing binary in the General Catalog of Variable Stars. The new data presented here for V532 Oph reveal the power of high-quality, high-cadence, all-sky photometric surveys, such as ASAS-3, to identify new RCB candidates on the basis of light-curve data alone, now that they have been collecting data for durations sufficiently long to reveal multiple declines. Despite their small numbers, RCB stars may be of great importance in understanding the late stages of stellar evolution. In particular, their measured isotopic abundances imply that many, if not most, RCB stars are produced by WD mergers, which may be the low-mass counterparts of the more massive mergers thought to produce type Ia supernovae. Therefore, establishing the population of RCB stars in the Galaxy will help constrain the frequency of these WD mergers.