Utilizing the mixed-ligand strategy, a novel fourfold-interpenetrated 3D homochiral metalorganic framework (1) with rare pair quadruple-stranded helices was assembled from bpee (1,2-bis(4-pyridyl)ethylene) and NCG (N-carbamyl-l-glutamate). Changing the carbamyl substituent of NCG with benzoyl group (NBzG: N-benzoyl-l-glutamate), a non-interpenetrated 3D homochiral coordination polymer (2) composed of alternate right-handed and left-handed single helix was obtained. When p-tolylsulfonyl substituent was used instead, an interesting homochiral linear structure (3) was formed from mixed-ligand bpee and NTsG (N-p-tolylsulfonyl-l-glutamate), with all individual NTsG being lined up orderly. The steric hindrance of N-substituent of l-glu has a tremendous impact on the construction of these diverse frameworks. Complexes 13 display second harmonic generation (SHG) efficiencies, which are approximately 0.32, 0.45, and 0.55 times as much as that of KDP powder.