The chiral resolution and separation of enantiomers is of great significance in both life science and pharmaceutical industry. Herein, we empoly butanol solvent isomerism and metal ion-coordintion to target chiral spontaneous resolution through chiral amplification forming superhelix. In Ni/ Rac-BrpempH 2 system, cyan flake crystal compounds Meso-1C and light blue gel 2S were generated from the reaction of NiSO 4·6H 2O and racemic 4-Br-(1-phenylethylamino)methylpho sphonate (4-BrpempH 2) under hydrothermal conditions at 100 °C for 2 days, in 20 % ethyl alcohol (EA)/H 2O and 40 % sec-butyl alcohol (SBA)/H 2O, respectively. Noteworthly, compound 2S is an aggregate of left-handed and right-handed nanohelices ( P&M) with the diameter about 60 nm and the pitch of 50 nm, which indicated chiral self-resolution was occured. Further to obtain a homochiral macroscopic helix, D/L-phephenylalanine (D-/L-Phe) or D-/L-Pipecolinic acid (D-/L-Pca) are added to the reaction system. Interestingly, the right-hand superhelices ( 2S-M) were obtained at the present of L-Phe additive, the left-hand superhelices ( 2S-P) at the present of D-Phe additive. However, when chiral Pca is used as a chiral additive, the opposite result to the above occurs, i.e., the addition of D-Pca results in a left-handed helix ( 2S-P) and vice versa for a right-handed helix ( 2S-P). In this case, the cosolvent SBA and chiral additive play critical roles in chiral resolution. Furthermore, helical products 2S-P and 2S-M obtained from D-/L-Phe chiral resolving agents exhibited comparable recognition capacities for Trp enantiomers.This study offers a novel method for chiral resolution through chiral amplification and provides a new pathway for the design and self-assembly of chiral materials with controllable handedness, especially in coordination polymer systems.