Ab initio molecular dynamics simulations of shock loading on poly(p-phenylene terephthalamide) (PPTA) reveal stress release mechanisms based on hydrogen bond preserving structural phase transformation (SPT) and planar amorphization. The SPT is triggered by [100] shock-induced coplanarity of phenylene groups and rearrangement of sheet stacking leading to a novel monoclinic phase. Planar amorphization is generated by [010] shock-induced scission of hydrogen bonds leading to disruption of polymer sheets, and trans-to-cis conformational change of polymer chains. In contrast to the latter, the former mechanism preserves the hydrogen bonding and cohesiveness of polymer chains in the identified novel crystalline phase preserving the strength of PPTA. The interplay between hydrogen bond preserving (SPT) and nonpreserving (planar amorphization) shock release mechanisms is critical to understanding the shock performance of aramid fibers.