This study reports the result of sodium citrate induced exopolymer extraction on the photocatalytic thin film (TiO2) pretreatment efficiency of waste activated sludge (WAS). TiO2 is immobilized through DC spluttering method followed by annealing process. The exopolymer removal of 94.2% by sodium citrate (0.05 g/g SS) promotes better disintegration. This TiO2 thin film efficiently extricate the intracellular components of exopolymer extracted sludge at 50 min increasing the solubilization to 19.33%. As a result, the exopolymer extracted sludge shows high methane generation (0.24 gCOD/gCOD) than the other (pretreated sludge without exopolymer removal - 0.12 gCOD/gCOD and raw sludge without treatment - 0.075 gCOD/gCOD). The methane generated in sodium citrate induced TiO2 thin film pretreated sludge is 398.99 kWh. In cost analysis, it gives net cost of -57.46 USD/ton of sludge. In addition, the proposed method also accounts 51.3% of solid reduction.