The present work reports a new type of optically active biobased hollow polymer particles (OABHPs) starting from a commonly available biophenylpropene transanethole (ANE). To prepare the OABHPs, ANE and maleic anhydride (MAH) underwent precipitation copolymerization in the presence of particulate template as cores, thereby forming core/shell particles. Subsequently removing the cores provided hollow particles, which were then chiralized with chiral agents (R- and S-1-phenylethylamine) and (R- and S-cyclohexyalethylamine) to fabricate the designed OABHPs. The as-prepared particles were characterized by SEM, TEM, elemental analysis, CD, and FT-IR measurements. The chiral particles' enantioselectivity was further explored by using them as chiral adsorbent toward D- and L-alanine and (-)-cinchonidine and (+)-cinchonine. The optically active hollow particles showed good enantiomeric excess (e.e.) toward racemic alanine. The study not only opens up a new approach for preparing chiral polymer materials, but also provides a versatile platform for making a full use of biomass to develop advanced functional materials.