Solar vapour generation is an efficient way of harvesting solar energy for the purification of polluted or saline water. However, water evaporation suffers from either inefficient utilization of solar energy or relies on complex and expensive light-concentration accessories. Here, we demonstrate a hierarchically nanostructured gel (HNG) based on polyvinyl alcohol (PVA) and polypyrrole (PPy) that serves as an independent solar vapour generator. The converted energy can be utilized in situ to power the vaporization of water contained in the molecular meshes of the PVA network, where water evaporation is facilitated by the skeleton of the hydrogel. A floating HNG sample evaporated water with a record high rate of 3.2 kg m(-2) h(-1) via 94% solar energy from 1 sun irradiation, and 18-23 litres of water per square metre of HNG was delivered daily when purifying brine water. These values were achievable due to the reduced latent heat of water evaporation in the molecular mesh under natural sunlight.