Hydroxyl dicarboxylic acids (OHDCA) are ubiquitous in the atmosphere as an important constituent of secondary organic aerosol, yet the formation mechanisms remain unclear. At an urban background site on the coast of South China, we observed notable levels of OHDCA, with the highest concentration of malic acid (a typical OHDCA species) reaching 533 ng m⁻³. In the coastal air, the correlation between OHDCA and sulfate was better (R² = 0.48) in the period when the relative humidity was higher and the sulfate size distribution was in a droplet mode, fitting the features of aqueous formation. In the short‐range continental air, a significant rise in OHDCA levels from morning through early afternoon (588 ng m⁻³) was observed under marked daytime increment of ozone that was corrected for titration loss (O₃_corr, sum of ozone and nitrogen dioxide). In addition, good correlation between OHDCA and O₃_corr was identified in this period, illuminating the role for gas‐phase photochemistry in regulating OHDCA formation. Therefore, the elevated OHDCA was likely attributed to aqueous photooxidation, and the dominant factors varied under different atmospheric conditions. The precursors of OHDCA could be derived from biogenic emissions, as indicated by the correlations of OHDCA with 2‐methylglyceric acid (bihourly data) and isoprene and monoterpenes (daily average data). However, anthropogenic aromatics might also be involved in OHDCA formation, especially in the short‐range continental air. The formation mechanisms probed through observational evidence will be an important reference for rectifying simulations of OHDCA and its impact on air quality and climate.