The refining of the crude palm oil (CPO) generates the palm oil refinery effluent (PORE). The presence of high contents of biochemical oxygen demand (BOD), chemical oxygen demand (COD), turbidity, and suspended solids (SS) in PORE encourages the determination of an effective treatment process to minimize the environmental pollution and preserve aquatic life. In the present study, a biodegradable natural polymer, namely tannin, was utilized as a coagulant to treat PORE. The coagulation experiment was conducted using a jar test apparatus. The tannin coagulation efficiency was evaluated based on the BOD, COD, turbidity, and SS removal from PORE by varying the tannin dose (50–300 mg/L), pH (pH 4–10), treatment time (15–90 min), and sedimentation time (15–90 min). It was found that the maximum removal of BOD, COD, turbidity, and SS was 97.62%, 88.89%, 93.01%, and 90.21%, respectively, at pH 6, a tannin dose of 200 mg/L, 60 min of coagulation time, and 60 min of sedimentation time. Analyses of isotherm models revealed that the Freundlich isotherm model was well fitted with the coagulation study. Kinetics studies show that the pseudo-second-order kinetics model was the well-fitted kinetics model for the BOD, COD, turbidity, and SS removal from PORE using tannin as a polymeric coagulant. The determination of thermodynamics parameters analyses revealed that BOD, COD, turbidity, and SS removal from PORE was spontaneous, exothermic, and chemical in nature. The finding of the present study shows that tannin as a natural polymeric coagulant would be utilized in PORE treatment to avoid toxic sludge generation.