Stable isotopes of hydrogen are a prerequisite for many industrial and scientific applications and require their ready supply on a large scale. Herein, we explore the chemical affinity-assisted separation of D-2 from a hydrogen isotopic mixture using calcium-rich porous carbon derived from onion peel. A sustainable physical activation using CO2 of onion-peel-derived carbon led to nanoporous carbon formation with a specific surface area of 433 m(2) g(-1) and a total pore volume of 0.27 cm(3) g(-1) along with a calcium composition of 17 wt% without using any calcium precursor. Calcium increases the chemical affinity of synthesized materials towards D-2, evidenced by the observation of a higher uptake for D-2 than H-2 in gas sorption and thermal desorption spectroscopy studies. Additionally, a promising D-2/H-2 selectivity of 5.6 at 40 K and a desorption energy difference of 2.31 kJ mol(-1) further support the higher binding strength for D-2, which endows its separation from the isotopic mixture. Hence, the current approach of using biowaste provides an environmentally friendly alternative for biowaste management in addition to a promising isotope separation candidate.