Lithium-selenium (Li–Se) batteries represent a promising energy storage system due to the relatively high electronic conductivity and high volumetric energy density of Se as a cathode. The design of porous carbon with tunable structure and low cost is a key to enabling Se cathodes for high-performance Li–Se batteries. In this study, hierarchically microporous activated carbon (AC) was fabricated from waste coffee grounds through a carbonization and KOH-activation process. Despite the simple synthesis process, the optimized AC (AC-700) had a high surface area of 1355 m2 g−1 and a large microspore volume of 0.52 cm³ g−1. The Se/AC-700 cathode showed a reversible capacity of 655 mAh g−1 after 100 cycles at 0.1C in Li–Se batteries based on a carbonate electrolyte. Moreover, the Se/AC-700 cathode demonstrated excellent cyclic performance over 400 cycles without appreciable capacity decay. The main reason for the good battery performance was attributed to fast electron transfer and Li-ion diffusion in Se confined in the microporous carbon of AC-700. It is expected that this work will shed light on the development of low-cost and stable Se cathodes for high-energy Li–Se batteries.