A novel macroporous silica‐based 2,6‐bis(5,6‐dibutyl‐1,2,4‐triazine‐3‐yl)pyridine (BDBTP) material, BDBTP/SiO2‐P, was prepared through impregnation and immobilization of BDBTP and octanol into the pores of the SiO2‐P particles. The adsorption of 10 typical fission and nonfission elements contained in highly active liquid waste (HLW) onto BDBTP/SiO2‐P was investigated by examining the effect of contact time and the HNO3 concentration in the range of 0.1–5.0 M. Pd(II), a weak Lewis acid and an electron‐pair acceptor, was strongly complexed with nitrogen, a weak Lewis base and an electron‐pair donor. BDBTP/SiO2‐P showed excellent adsorption ability and high selectivity for Pd(II) over all the tested metals. The separation of Pd(II) from a simulated HLW was performed by BDBTP/SiO2‐P packed column. Pd(II) was effectively eluted with 0.2 M thiourea and separated from the others. It demonstrated that in HNO3, application of the macroporous silica‐based BDBTP/SiO2‐P material in partitioning and recovery of Pd(II) from HLW is promising. © 2010 American Institute of Chemical Engineers AIChE J, 2010