Postpolymerization modification of polystyrene (PS) can afford numerous value-added materials with different functions and applications, but it has been hampered by the lack of efficient methods. We report herein a highly efficient and para-selective conversion of the C-H bonds of the aromatic ring of PS into diverse functional groups using a combination of thianthrenation and thio-Suzuki-Miyaura coupling reaction. Notably, the thianthrenation efficiency of PS is as high as 99% and the degree of thianthrenation can be conveniently controlled using stoichiometric tuning of the amount of thianthrene-S-oxide added, resulting in 24-99 mol % thianthrenation. In the subsequent thio-Suzuki-Miyaura coupling reaction, 18 functionalized PS containing various functional groups (-CH2OH, -OMe, -SMe, -OTBS, -CH3, -NHBoc, -OCOMe, -CHO, -COMe, -Si(Me)3, etc.) were successfully prepared with a high degree of functionalization (64-99 mol %). The obtained functionalized PS can be readily converted into diverse functional materials, including solid-phase synthesis resins, aggregation-induced emission fluorophores, as well as ionomer binders and ion-exchange membranes for energy conversion devices. This method imparts diverse functionality onto PS with extremely high efficiency and selectivity, providing a versatile platform to transform existing commodity PS plastics into high-performance materials.