Adsorption of Reactive Black 5 and Congo Red from aqueous solution by coffee waste modified with polyethylenimine was investigated. The removal percentages of both dyes increased with amount of polyethyleneimine in the modified adsorbent. Characterization revealed that polyethyleneimine modification improved the adsorbent surface chemistry, while slight improvement of adsorbent textural properties was also observed. The adsorbent's excellent performance was demonstrated by high removal percentages towards the anionic dyes in most experimental runs. The modelling result showed that anionic dyes adsorption occurred via monolayer adsorption, and chemisorption was the rate-controlling step. The adsorbent possesses higher maximum adsorption capacity towards Reactive Black 5 (77.52 mg/g) than Congo Red (34.36 mg/g), due to the higher number of functional groups in Reactive Black 5 that interact with the adsorbent. This study reveals the potential of adsorbent derived from coffee waste in textile wastewater treatment. Furthermore, surface chemistry modification is proven as an effective strategy to enhance the performance of biowaste-derived adsorbents.