Solar-blind photodetectors have widespread applications due to the unique merit of a “black background” on the earth. However, most solar-blind photodetectors reported previously exhibited quite low rejection ratios (R200nm/R280nm< 103) and were interfered with by light longer than 280 nm. Herein, by an ambient pressure chemical vapor deposition (CVD) method, large-area, clean, and uniform two-dimensional (2D) multilayer h-BN films with different thicknesses have been successfully synthesized on Au foils. The synthesized multilayer h-BN film is transparent to light longer than 280 nm, showing excellent optical and optoelectronic properties to weak solar-blind light (μW/cm2). This sensitive solar-blind h-BN photodetector exhibits ultrahigh rejection ratios (R220nm/R280nm> 103and R220nm/R290nm> 104), a low dark current (102fA), and a large detectivity (3.9 × 1010Jones). It is noteworthy that the rejection ratio (R220nm/R290nm) here is superior to most of those previously reported based on traditional semiconductors. This large-scale, clean, and uniform multilayer h-BN film will contribute to the progress of next-generation optoelectronic devices.