Solar-driven water purification has been deemed a promising technology to address the issue of clean water scarcity. However, traditional solar distillers often suffer from low evaporation rates under natural sunlight irradiation, while the high costs of the fabrication of photothermal materials further hinders their practical applications. Here, through the harnessing of the complexation process of oppositely charged polyelectrolyte solutions, a polyion complex hydrogel/coal powder composite (HCC)-based highly efficient solar distiller is reported. In particular, the influence of the charge ratio of polyanion-to-polycation on the solar vapor generation performance of HCC has been systematically investigated. Together with a scanning electron microscope (SEM) and the Raman spectrum method, it is found that a deviation from the charge balance point not only alters the microporous structure of HCC and weakens its water transporting capabilities, but also leads to a decreased content of activated water molecules and enlarges the energy barrier of water evaporation. As a result, HCC prepared at the charge balance point exhibits the highest evaporation rate of 3.12 kg m−2h−1under one sun irradiation, with a solar–vapor conversion efficiency as high as 88.83%. HCC also exhibits remarkable solar vapor generation (SVG) performance for the purification of various water bodies. In simulated seawater (3.5 wt% NaCl solutions), the evaporation rate can be as high as 3.22 kg m−2h−1. In acid and alkaline solutions, HCCs are capable of maintaining high evaporation rates of 2.98 and 2.85 kg m−2h−1, respectively. It is anticipated that this study may provide insights for the design of low-cost next-generation solar evaporators, and broaden the practical applications of SVG for seawater desalination and industrial wastewater purification.