Green roofs (GRs) have been researched for decades, yet their implementation remains constrained due to several reasons, including their limited appeal to policymakers and the public. Biochar, a carbon-rich material, has been recently introduced as an amendment to GR substrate to enhance the performance of GRs through reduced runoff volume, improved runoff quality, and increased soil fertility. This paper aims to investigate the impact of biochar amendment on the hydrological performance of newly established GRs. Six 1 m × 1 m GR test beds were constructed, comprising of five biochar-amended GR test beds, and one conventional test bed (without any biochar in its substrate). The water retention capacity and runoff outflow delay of the six test beds were studied with the application of artificial rainfall using a nozzle-based simulator. Biochar was found to increase the water retention capacity and effectively delay runoff outflow in the biochar-amended GRs. After nine artificial rainfall events of 110.7 mm rainfall in total, 39.7 to 58.9 L of runoff was retained by the biochar-amended GRs as compared to 37.9 L of runoff retained by the conventional GR. Additionally, the test bed without biochar quickly started releasing runoff after 300 to 750 s, whereas test beds with fine biochar particles could delay runoff outflow by 700 to 1100 s. The performance of the non-biochar and biochar-amended test beds varies according to the values of biochar-related variables such as biochar particle sizes, amendment rates, and application methods. The observational data illustrated that the GR test bed with medium biochar particles applied to the bottom layer of the GR substrate was the optimal biochar-GR design. This selection was determined by the combined performance of high retention rates, long runoff outflow delays, and few other factors, such as lesser loss of biochar caused by wind and/or water.