Two novel kinds of dopamine-modified alginate beads were developed by using titanium(IV) coordination or self-polymerization, besides the conventional Ca2+ ion cross-linking. Alginate was modified with dopamine (Alg(DA)) via EDC/NHS chemistry. Fourier transform infrared spectroscopy (FTIR) and circular dichroism (CD) characterization confirmed that dopamine was covalently attached preferentially to the mannuronic acid residues of alginate; thus, gel-forming ability of the as-prepared Alg(DA) was well retained. The titanium(IV) coordination-reinforced alginate beads [Ca-Ti(Alg(DA))] were prepared by cross-linking with Ti4+ and Ca2+. Covalently cross-linking-reinforced alginate beads (Ca-Alg(PDA)) were also prepared by self-polymerization of dopamine and cross-linking with Ca2+. The swelling of Ca-Alg(PDA) and Ca-Ti(Alg(DA)) were both obviously inhibited, and the mechanical properties were enhanced by 3 times compared to those of Ca-Alg beads. The as-prepared beads were utilized for immobilization of alcohol dehydrogenase (YADH). The immobilization efficiency of Ca-Ti(Alg(DA)) and Ca-Alg(PDA) reached up to 100% and 89%, respectively, both notably higher than that of Ca-Alg (67.4%). Stabilities of the immobilized YADH in Ca-Alg(PDA) and Ca-Ti(Alg(DA)) toward pH, storage, and recycling were all improved compared with those immobilized in Ca-Alg.