Halide perovskites have attracted tremendous attention as semiconducting materials for various optoelectronic applications. The functional metal-halide octahedral units and their spatial arrangements play a key role in the optoelectronic properties of these materials. At present, most of the efforts for material exploration focus on substituting the constituent elements of functional octahedral units, whereas designing the spatial arrangement of the functional units has received relatively little consideration. In this work, via a global structure search based on density functional theory (DFT), we discovered a metastable threedimensional honeycomb-like perovskite structure with the functional octahedral units arranged through mixed edgeand corner-sharing. We experimentally confirmed that the honeycomb-like perovskite structure can be stabilized by divalent molecular cations with suitable size and shape, such as 2,2′-bisimidazole (BIM). DFT calculations and experimental characterizations revealed that the honeycomb- like perovskite with the formula of BIMPb2I6, synthesized through a solution process, exhibits high electronic dimensionality, a direct allowed bandgap of 2.1 eV, small effective masses for both electrons and holes, and high optical absorption coefficients, which indicates a significant potential for optoelectronic applications. The employed combination of DFT and experimental study provides an exemplary approach to explore prospective optoelectronic semiconductors via spatially arranging functional units.