The growth of three-dimensional covalent organic frameworks (3D COFs) with new topologies is still considered as a great challenge due to limited availability of high-connectivity building units. Here we report the design and synthesis of novel 3D triptycene-based COFs, termed JUC-568 and JUC-569, following the deliberate symmetry-guided design principle. By combining a triangular prism (6-connected) node with a planar triangle (3-connected) or another triangular prism node, the targeted COFs adopt unreported ceq or non-interpenetrated acs topology, respectively. Both materials show permanent porosity and impressive performance in the adsorption of CO2 (~ 98 cm3/g at 273 K and 1 bar), CH4 (~ 48 cm3/g at 273 K and 1 bar), and especially H2 (up to 274 cm3/g or 2.45 wt% at 77 K and 1 bar), which is highest among porous organic materials reported to date. This research thus provides a promising strategy for diversifying 3D COFs based on complex building blocks and promotes their potential applications in energy storage and environment-related fields.