Alginate-based oil-in-water (O/W) emulsion Liquid Marbles (LMs) were successfully created by hybridizing stearate calcium and calcium chloride microparticles. The controlled release of a bio-functional hydrophobic volatile component (limonene) by the emulsion LM shells was achieved. The outer diameter of the LMs was uniform from 3.0 to 3.3 mm. Four types of LMs were examined: O/W emulsion droplet (NED), O/W emulsion LM (ELM), sodium-alginate O/W emulsion LM (AlgLM), and sodium alginate-shelled O/W emulsion LM (GELM). The amount of released limonene initiated after 60 min from the ELM was ca. 0.70 folds lesser than that from the NED. The released amount from the AlgLM was 0.47 folds less than that from the ELM. The participation of the limonene between the dispersed limonene phase and the aqueous alginate phase in the AlgLM was influenced by solubilized sodium alginate. The released amount from the GELM was significantly low. It was 0.032 folds less than that from the ELM. On the outer surface of the GELM, calcium chloride powder coexisted with calcium stearate. The calcium chloride powder on the outer surface gradually solubilized into the aqueous sodium alginate phase and quickly formed a cross-linked alginate shell. The mass transfer of the released limonene was inhibited both by the high viscosity of the alginate phase and the cross-linked alginate shell. LMs prepared from biocompatible materials showed promising abilities for the controlled release of limonene. The alginate-based O/W emulsion LMs can facilitate the controlled release of comprehensive volatile bioactive components in the forthcoming sustainable-material era.