In order to prevent health risk from potential exposures to phthalates, a glow discharge plasma (GDP) process was applied for phthalate degradation in aqueous solution. The results revealed that the phthalate derivatives 4-hydroxyphthalic acid, 4-methylphthalic acid and 4-tert-butylphthalic anhydride could be degraded efficiently in GDP process (498 V, 0.2 A) with high removal efficiencies of over 99% in 60 minutes. Additionally, pyrite as a promising heterogeneous iron source in the Fenton reaction was found to be favorable for GDP process. The phthalate degradation reaction could be significantly enhanced by the continuous formation of •OH and the inhibition of the quenching reaction in the pyrite Fenton system due to the constant dissolution of Fe(II) from pyrite surface. Meanwhile, the initial pH value showed little impact on the degradation of phthalates and the energy efficiency of GDP system for phthalate degradation ranged between 0.280 × 10−9 and 1.210 × 10−9 mol/J, which is similar to the GDP system with phenol, bisphenol A and methyl tert-butyl ether as the substrates. Further, the X-ray diffraction and scanning electron microscopy with energy dispersive X-ray spectroscopy analyses indicated that the pyrite was relatively stable in GDP system and there was no obvious polymeric compound formed on the catalyst surface. Overall, this GDP process offers high removal efficiency, simple technology, considerable energy efficiency and the applicability to salt-containing phthalate wastewater.