The title compound [(VO)(H2O)2(SeO3)]2[(H2pipe)SO4] was synthesized under hydrothermal condition with VOSO4, piperazidine (pipe), and SeO2, and its crystal structure was established using single-crystal X-ray diffraction method. The title compound was characterized with IR□Fluorescence. The crystal data: P-1 (No. 2), a = 8.633(2) Å, b= 9.223(2) Å, c= 12.508(3) Å, α =109.28(3)°, β =90.42(3)°, γ = 107.79(3)°, Mr = 644.08, V=888.5(3) Å3, Z=2, Dc = 2.407 g cm−3, μ =5.350 mm−1, F(000)=632. The structure of the title compound consists of an infinite neutral ladder chain, which is built up from VO6 octahedral and SeO3 pyramidal units sharing vertices, and organic salt. The biprotonized pipe (piperazidine) and SO42− interact with one another and the inorganic chain through strong hydrogen bonds N–H···O or O–H···O to give a 3D structure. Hydrogen bonds play a role of stabilization structure.