We present here the synthesis of one enantiomeric pair of metal organic framework materials comprised of a unique multioriented double-helix structure from an achiral spirocenter ligand. Our study clearly shows that the chiral MOF material encompasses concurrently multiple nonlinear-optical functions in the solid state: the noncentrosymmetric structural feature brings the chiral MOF high second-harmonic-generation efficiency; the incorporation of the spirocenter ligand can efficiently produce two-photon-excited photoluminescence with a larger-action cross-sectional value.