The utilization of powdered photocatalysts can cause problems such as agglomeration and difficulty in separation in conventional applications. In this work, deposition of photocatalyst particles on a co-polymeric network was suggested to solve this issue. For this purpose, ferrite type perovskite BiFeO3 particles were immobilized on the sulphonated polystyrene-divinyl benzene seeds via a facile impregnation process and the heterostructured catalyst (BFO@ co-STR/DVB) exhibited boosted removal performance towards tetracycline antibiotic. The co-polymer itself showed attractive adsorption (93% removal) towards tetracycline due to the robust π–π stacking or hydrophobic relationship. The photocatalytic performance of optimal BFO@co-STR/DVB catalyst had the greatest value of apparent rate constant (0.037 min-1), which was 6.16 times higher than that for bare BiFeO3 (0.006 min-1). Moreover, the heterostructured photocatalyst displayed the highest catalytic efficiency as 98.5% which was mainly assigned to the synergetic effect of adsorption and photocatalysis. Therefore, detailed adsorption mechanism was examined by applying three kinetic models and the pseudo-second order model (qe=88.9 mg/g; R2=0.993) was fitted well describing well the adsorption. The impact of perovskite amount on the polymer structure was also investigated. Apart from tetracycline molecule, the photocatalytic activity of the heterostructured catalyst with respect to different pharmaceutical (isoniazid) was also investigated and the adsorptive removal of isoniazid over the co-STR/DVB polymer was calculated as 80.0% while it significantly increased to 98.2% in the BFO@co-STR/DVB photocatalytic system. This study demonstrated the effective utilization of the perovskite deposited co-polymeric network in the field of “photocatalysis”.