Biochar prepared from crop straw is an economical method for adsorbing bromocresol green (BCG) from textile industrial wastewater. However, there is limited research on the adsorption mechanism of biochar for the removal of BCG. This study utilized cucumber straw as raw material to prepare biochar with good adsorption potential and characterized its physicochemical properties. Through adsorption experiments, the effects of solution pH, biochar dosage, and initial dye concentration on adsorption performance were examined. The adsorption mechanism of cucumber straw biochar (CBC) for BCG was elucidated at the molecular level using adsorption kinetics, adsorption isotherm models, and density functional theory (DFT) calculations. Results show that the specific surface area of the CBC is 101.58 m²/g, and it has a high degree of carbonization, similar to the structure of graphite crystals. The presence of aromatic rings, –OH groups, and –COOH groups in CBC provides abundant adsorption sites for BCG. The adsorption process of CBC for BCG is influenced by both physical and chemical adsorption, and can be described by the Langmuir isotherm model, indicating a monolayer adsorption process. The theoretical maximum monolayer adsorption capacity (q_m) of BCG at 298 K was calculated to be 99.18 mg/g. DFT calculations reveal interactions between BCG and CBC involving electrostatic interactions, van der Waals forces, halogen–π interactions, π–π interactions, and hydrogen bonds. Additionally, the interaction of hydrogen bonds between BCG and the –COOH group of biochar is stronger than that between BCG and the –OH group. These findings provide valuable insights into the preparation and application of efficient organic dye adsorbents.