Conjugated π-surfaces are ubiquitous in molecules and materials. However, large π-surfaces up to a few nanometers in size are difficult to construct in an atomically precise manner. They tend to aggregate because of strong π−π interactions, resulting in notorious problems for both purification and spectroscopic investigations. Here, by contrast, we report the design, synthesis, and full characterizations of a nonplanar nanographene 1, which has a large, precise, and nonstacked πsurface. It is soluble in common organic solvents and allows for thorough investigations. The structure of 1, comprising 85 fused rings with an extended π-surface of 3 nm in size, is unambiguously confirmed by singlecrystal X-ray diffraction. Unusual electronic structures, record-high nearinfrared absorption, pronounced magnetic shielding, and ultrastrong heteromolecular van der Waals complexations are demonstrated, enabling us to establish a clear structure−property relationship, which has been elusive for decades. These results have broad implications for studying and understanding various phenomena and processes relevant to both discrete and interacting π-surfaces.