The textile dyeing and manufacturing industry is the major producer of significant amounts of wastewater that contain persistent substances such as azo dyes that require adequate remediation measures. Far ultraviolet at 222 nm light may provide an advantage for contaminants degradation as compared to conventional UV sources (254 nm). In this paper, the degradation of reactive black 5 (RB5) in artificial wastewater has been performed using a 222 nm Kr/Cl2 excimer source under direct photolysis and an advanced oxidation process using TiO2/H2O2. The solution pH, catalyst concentration, 222 nm intensity, initial concentration of dye, and addition of H2O2 influence the degradation rate constant. The molar absorption coefficient, quantum yield of RB5 at 222 nm and the electrical energy per order (EEO) from different treatment methods have been reported. RB5 shows 1.26 times higher molar absorption at 222 nm than at 254 nm. The EEO for excimer-222/H2O2 ($$\sim$$
∼
13 kWh/m3) is five times lower than that of the excimer-222/TiO2 process, which makes the process energy efficient. The degradation of wastewater has been carried out at three distinct pH values (2, 6, and 10), and the pH level of 10 exhibited the highest degree of degradation. The degradation rate in the alkaline medium is 8.27 and 2.05 times higher than in the acidic or ambient medium. Since textile effluent is highly alkaline, this result is significant, as no neutralization of the wastewater is required, and direct treatment is possible. A possible degradation pathway has been established based on Fourier transform infrared spectroscopy (FTIR) and high resolution mass spectroscopy (HRMS) analysis. The phytotoxicity of the treated wastewater has also been evaluated for its suitability for reuse in agriculture. The study reveals that the excimer-222/H2O2 treated wastewater significantly enhanced the germination percentage of Raphanus sativus seed (97%) compared to dye wastewater-grown seeds (75%). This work offers crucial information for future studies on the direct and indirect photolysis of azo dyes, as well as insight into the process of RB5 degradation under Kr/Cl2 excimer radiation.