Lead-free halide perovskites have attracted widespread research interest due to their excellent optoelectronic properties and environmental friendliness. As one of the bismuth iodide compounds, Cs3Bi2I9 perovskite has been extensively explored in the field of photovoltaic devices and radiation detectors due to their non-toxic lead-free components and excellent stability. In this work, we successfully grow large-sized Cs3Bi2I9 single crystals (SC) with (l00) and (00l) crystal exposure facets by inverse temperature crystallization method. Under 525 nm light illumination with the intensity 15 mW cm−2 and 7 V bias, the (l00) Cs3Bi2I9 SC shows 2 times higher photocurrent, 3.6 times higher responsivity, and 2.8 times higher detectivity than the (00l) Cs3Bi2I9 SC, respectively. Superior response time in the scale of millisecond is obtained in both (l00) and (00l) Cs3Bi2I9 SCs. Based on the first-principle calculation, the (l00) SC possesses a higher charge distribution density and a wider dispersion distribution than (00l) SC, suggesting that more electrons in the (l00) SC can be excited in a wider range. The tighter arrangement of Cs+ and [BiI6]− octahedra in the (l00) SC than (00l) SC leads to the anisotropic photoelectric performance in (l00) and (00l) Cs3Bi2I9 SCs. Our results provide a strategy for the oriental growth of Cs3Bi2I9 SCs and the design of anisotropic optoelectronic devices with excellent performance.