The macroporous silica synthesis system with the ABC triblock terpolymer poly(ethylene oxide)-block-polystyrene-block-poly(tert-butyl acrylate) (denoted as OSA) as template and tetraethyl orthosilicate as silica source under acidic conditions in a mixture solvent of tetrahydrofuran and H2O has been investigated, and two synthesis-field phase diagrams are plotted. Eight different structures varied from normal-phase (oil in water) cage-type (n-C), normal-phase 2D hexagonal (n-H), and lamellar (L) to unique inverse-phase (water in oil) hyperbolic-surface (i-HS) structures, including the shifted double-diamond (i-SDD), single-gyroid (i-SG), and shifted double-primitive (i-SDP), inverse-phase 2D hexagonal (i-H) and inverse-phase micellar (i-M) structures, have been formed by varying the degree of polymerization of the hydrophobic blocks in OSA. From the two-component phase diagram, it can be concluded that the macroporous structures formation is affected by the packing parameter p and the segregation product (chi N) of the hydrophilic and hydrophobic blocks. With an increase in p, the structures n-C and n-H were found in the range of low chi N, whereas the structures i-HS, i-H, and i-M were found in the range of higher chi N, while L is in between. In the three-component phase diagram, different volume fraction ratios (VFR) of the hydrophobic/hydrophilic block (S/O, A/O) and those of hydrophobic/hydrophobic block (S/A) in this co-assembly system divided the resultant ordered structures in various regions. The n-C, n-H, and L structures were found in low VFRs of S/O and A/O; i-H and i-M structures were formed in high VFRs of S/O and A/O. The formations of the i-HS structures including i-SDD, i-SDP, and i-SG are depending on low VFRs regions of S/O and S/A with similar packing parameter.