Deep-ultraviolet nonlinear optical (deep-UV NLO) crystals are of worldwide interest for the generation of coherent light with wavelength below 200 nm by the direct second-harmonic generation (SHG) output from solid-state lasers. The unprecedented deep-UV NLO phosphates representing their own structure types, Ba3P3O10Cl (BPOC), Ba3P3O10Br (BPOB), have been discovered, which display moderate powder SHG intensities in type I phase matchable behaviors with a short UV cutoff edge of 180 nm (measured by a single crystal, one of the shortest values among phosphates to date). Insightfully, the geometry and polarization of the C-1-P3O105- building unit are affected by the crystal packing. DFT calculations and cutoff energy dependent SHG coefficient analyses reveal that the SHG origin is from the cooperation of asymmetric C-1-P3O105- anion, Ba2+ cation, and Cl-/Br- anion.