H2SO4 has an effect on the sorption of organic contaminants by coking coal (CC) in wastewater. This paper focused on the effect of pH on the removal of chemical oxygen demand (COD), phenols and ammonia. UV-vis spectra, Fourier transform infrared spectra, zeta potential and Brunauer, Emmett and Teller (BET) analysis were investigated to characterize the changes of CC properties and coking wastewater (CW) at different pH values. The results showed that the COD and phenol removal efficiencies increased with decreasing pH value, while the ammonia removal efficiency was decreased gradually. A new transmittance band in the region of 340–600 cm−1 was observed in UV-vis spectra of CW in acidic condition. The absolute value of the zeta potential as the solution was gradually increasing with the increasing of pH value. Surface area and total pore volume of CC which was immersed in acidic solutions measured by BET were much higher than that of raw CC. CC has a greater adsorption capacity to organic pollution in the acidic solution mainly by van der Waals forces and hydrogen bonding.