A wet electrostatic precipitator (WESP) has much higher capture rate for fine particulate matter, PM2.5, than a traditional dry type electrostatic precipitator does. In order to make full use of existing dust removal equipment and reduce the emissions of smoke and dust to zero, a combination of chemical coagulation and humidification coagulation is proposed using a WESP. The results show that the addition of chemical coagulant can promote the coagulation of coal-fired dust particles. After the addition of pectin (PG), the median diameter of dust particles increases from 28.19 μm to 45.28 μm. Water vapor humidification can promote the coagulation of dust particles. When the water vapor injection rate increases from 0 kg/h to 3.2 kg/h, the median diameter of dust particles increases from 28.19 μm to 36.45 μm. The synergistic effect of the coagulant and water vapor can enhance the chemical coagulation effect; when 1.0 × 10−2g/L PG and 3.2 kg/h water vapor synergize, the collection efficiency reaches 98.17%, and when 1.0 × 10−2g/L polyacrylamide (PAM) and 3.2 kg/h water vapor synergize, the collection efficiency reaches 96.68%. Both chemical coagulation and water vapor humidification can promote the condensation of coal dust, which is beneficial to improve the efficient capture of fine particles using WESP.