This study investigates the acidity of particulate matter with an aerodynamic diameter less than 2.5 μm (PM2.5) in Hanoi, the capital city of Vietnam, and its influencing factors by analyzing measured concentrations of water-soluble inorganic ions (WSIIs) in 107 24-h samples collected between June 2021 and February 2022. The average sulfate, nitrate, and ammonium concentrations were 5.79, 3.55, and 5.46 μg m−3, respectively. Among the samples, 83 exhibited alkaline aerosols characterized by elevated ammonium-to-sulfate molar concentration ratios (ASMCR) ranging from 2.3 to 9.6, while 24 showed acidic characteristics with ASMCR ranging from 0.5 to 2.5. By employing the Extended Aerosol Inorganic Model E-AIM III, with major WSIIs as the input parameters, the estimated aerosol acidity pH ranged from 8.6 to 10.9 for alkaline aerosols and below 4.5 for acidic aerosols. These variations in ASMCR and aerosol pH highlight the distinct acidic and alkaline aerosol source regions affecting Hanoi's PM2.5 by the monsoon air masses. The Potential Source Contribution Function (PSCF) maps of NH4+ and SO42− revealed the Northeast and Southeast monsoon upwind sources of acidic aerosols over China's Guangdong coastal region and Vietnam's offshore, respectively. Alkaline aerosols were observed during the Northeast and Southwest monsoons, with upwind sources originating in South China, Thailand, and Cambodia. The emergence of the ammonium-rich source areas in South China may be attributed to China's sustained emission control measures, targeting acidic SO2 and NOx emissions while leaving alkaline NH3 emissions largely unaffected. This research provided insights into the intricate relationships between regional emissions, long-range transport, and local meteorological-driven emissions, offering valuable guidance for effective air quality management in urban environments.