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Monoclinic phase Bi6Mo2O15 sub-microwires were fabricated by one-step molten salt method. These sub-microwires were found to be much more active than Bi2MoO6 in photocatalytic degradation of rhodamine B (RhB) under sunlight irradiation. The degradation velocity of Bi6Mo2O15 is 98% four times than Bi2MoO6 which might be attributed to its surface oxygen atoms surrounding Bi elements. In particular, the individual ultra-long (∼60 µm) Bi6Mo2O15 sub-microwire was employed as an ultraviolet photodetector, which shows an ultrahigh quantum efficiency of 2.95 × 107% under a wavelength of 254 nm illumination. This study provides a feasible alternative to development of nanocomposite photocatalysts with multi atom unit which manifest important photocatlytic and photoelectochemical applications. Keywords: Photocatalyst, RhB degradation, Photodetector, Quantum efficiency