Thermally insulating materials are commonly used to reduce energy consumption in buildings. Most commercial products possess only low thermal conductivities but poor insulating capabilities in the daytime with little sunlight reflectance and thermal emittance. It is challenging to achieve all traits in the same material. Herein, anisotropic boron nitride nanosheet (BNNS)/polyvinyl alcohol composite aerogels are developed using the unidirectional freeze-casting technique. Benefitting from the aligned porous structure, the composite aerogel with an optimal BNNS content exhibits a combination of an ultralow TC of 20.3 mW/mK in the through-thickness direction, a high solar-weighted reflectance of 95.0 % over the whole sunlight wavelength and a high emittance of above 93 % within the atmospheric transparency window. These exceptional thermo-optical properties enable the composite aerogel to maintain the interior temperature much cooler than commercially available foams, making them promising candidates as superinsulating envelopes for energy saving in buildings towards carbon neutrality.