A sound in-plant pollution control strategy can only be defined by paying due attention to bio-recalcitrance and toxicity. In this context the levels of toxicity and inert COD introduced to textile dyebath discharges by two alternative auxiliary chemicals, namely natural tannin (NT) and synthetic tannin (ST), were investigated. The effect of 40 minutes ozonation at 1,000 mg h(-1) at pH 3.5 on the segregated effluent streams containing the above-mentioned tannin formulations was evaluated in terms of changes in toxicity and recalcitrance. The effect of ozonation on the COD distribution of raw and ozonated NT and ST samples according to their molecular weight cut-offs was also assessed. Both untreated tannin formulations exerted high acute toxicity towards marine microalgae Phaeodactylum tricornutum. Moderate decrease in the toxicity levels of both tannins was observed upon ozonation. The raw NT formulation with a COD content more than twice that of its alternative raw ST had an initially inert soluble COD content of only 25 mg/L, while the initially inert COD was 135 mg/L for ST. As the initially inert soluble COD content of NT was considerably lower, this textile auxiliary did not need chemical pretreatment to improve its biodegradability. On the other hand, the initially inert soluble COD content of ST was reduced by 70% by ozone pretreatment. In terms of residual COD contents achievable after passing through a biological treatment system, raw NT and pretreated ST formulations yielded 100 and 95 mg/L COD, respectively. The highest proportion of COD (46% for NT and 88% for ST) was found in the < 1 kDa range. The same fraction increased to 93% for NT after ozonation, while for ST no significant change was observed in the COD distribution of the molecular weight cut-offs after ozonation.