<p><strong>Abstract.</strong> A PM<sub>2.5</sub>-capable aerosol chemical speciation monitor (Q-ACSM) was deployed in urban Nanjing, China, for the first time to measure in situ non-refractory fine particle (NR-PM<sub>2.5</sub>) composition from 20 October to 19 November 2015, along with parallel measurements of submicron aerosol (PM<sub>1</sub>) species by a standard Q-ACSM. Our results show that the NR-PM<sub>2.5</sub> species (organics, sulfate, nitrate, and ammonium) measured by the PM<sub>2.5</sub>-Q-ACSM are highly correlated (<i>r</i><sup>2</sup> &gt; 0.9) with those measured by a Sunset Lab OC<span class="thinspace"></span><span class="thinspace"></span>/<span class="thinspace"></span><span class="thinspace"></span>EC analyzer and a Monitor for AeRosols and GAses (MARGA). The comparisons between the two Q-ACSMs illustrated similar temporal variations in all NR species between PM<sub>1</sub> and PM<sub>2.5</sub>, yet substantial mass fractions of aerosol species were observed in the size range of 1–2.5<span class="thinspace"></span>µm. On average, NR-PM<sub>1−2.5</sub> contributed 53<span class="thinspace"></span>% of the total NR-PM<sub>2.5</sub>, with sulfate and secondary organic aerosols (SOAs) being the two largest contributors (26 and 27<span class="thinspace"></span>%, respectively). Positive matrix factorization of organic aerosol showed similar temporal variations in both primary and secondary OAs between PM<sub>1</sub> and PM<sub>2.5</sub>, although the mass spectra were slightly different due to more thermal decomposition on the capture vaporizer of the PM<sub>2.5</sub>-Q-ACSM. We observed an enhancement of SOA under high relative humidity conditions, which is associated with simultaneous increases in aerosol pH, gas-phase species (NO<sub>2</sub>, SO<sub>2</sub>, and NH<sub>3</sub>) concentrations and aerosol water content driven by secondary inorganic aerosols. These results likely indicate an enhanced reactive uptake of SOA precursors upon aqueous particles. Therefore, reducing anthropogenic NO<sub><i>x</i></sub>, SO<sub>2</sub>, and NH<sub>3</sub> emissions might not only reduce secondary inorganic aerosols but also the SOA burden during haze episodes in China.</p>