The characteristics and sources of PM2.5-O3 compound pollution were analyzed based on the high-resolution online monitoring data of PM2.5, O3 and volatile organic compounds(VOCs) observed in Tianjin from 2017 to 2019. The results showed that total PM2.5-O3 compound pollution was 34 days, which only appeared between March and September and slightly increased by year. The peak value of ρ(O3)(301-326 μg·m-3) appeared when ρ(PM2.5) ranged from 75 μg·m-3 to 85 μg·m-3. During PM2.5-O3 compound pollution, the average ρ(VOCs) was 72.59 μg·m-3, and the chemical compositions of VOCs were alkanes, aromatics, alkenes, and alkynes, accounting for 61.51%, 20.38%, 11.54%, and 6.57% of VOCs concentration on average, respectively. The concentration of the top 20 species of VOCs increased, among which the proportion of alkane species such as ethane, n-butane, isobutane, and isopentane increased; the proportion of alkenes and alkynes decreased slightly; and the proportion of benzene and 1,2,3-trimethylbenzene of aromatic hydrocarbons increased slightly. The ozone formation potential(OFP) contribution of alkanes, alkenes, aromatics, and alkynes were 19.68%, 39.99%, 38.08%, and 2.25%, respectively; the contributions of alkanes, alkenes, and aromatics to secondary organic aerosol(SOA) formation potential were 7.94%, 2.17%, and 89.89%, respectively. Compared with that of non-compound pollution, the contribution of alkanes and aromatics to OFP increased 13.8% and 4.3%, and that to SOA formation potential increased 2.3% and 0.2%, respectively. The contribution of alkenes to OFP and SOA formation potential decreased 9.4% and 15.6%, respectively, and the contribution of alkynes to OFP increased 7.7% in compound pollution. The contributions of main species such as 1-pentene, n-butane, methyl cyclopentane, isopentane, 1,2,3-trimethylene, propane, toluene, acetylene, o-xylene, ethylbenzene, m-ethyltoluene, and m/p-xylene to OFP increased, and that of isoprene to OFP decreased. The contribution of benzene, 1,2,3-trimethylbenzene, toluene, and o-xylene to the potential formation of SOA increased during compound pollution. Positive matrix factorization was applied to estimate the contributions of sources to OFP and SOA formation potential in compound pollution, solvent usage, automobile exhaust, petrochemical industrial emission, natural source, liquefied petroleum gas(LPG) evaporation, combustion source, gasoline evaporation, and other industrial process sources were identified as major sources of OFP and SOA formation potential; the contributions of each source to OFP were 21.9%, 16.9%, 16.7%, 12.4%, 8.3%, 7.7%, 2.9%, and 13.2%, respectively, and to SOA formation potentials were 46.8%, 14.4%, 7.1%, 11.9%, 5.9%, 6.6%, 1.6%, and 5.7%, respectively. Solvent usage, automobile exhaust, and petrochemical industrial emissions were main sources for PM2.5-O3 compound pollution.