Microorganisms have the ability to settle on nearly all man-made surfaces in contact with seawater and subsequently to form biofilm. Biofilms control and removal is necessary in the sectors of maritime transport, energy... In this work, we present the development of new pure calcium, zinc or copper alginate, but also mixed Ca/Cu and Ca/Zn alginate hydrogels. These materials have been evaluated for their potential inhibition of adhesion of two key biofilm-forming microalgae Halamphora coffeaeformis and Cylindrotheca closterium). All the tested materials have presented high adhesion inhibition about 80%). Copper-base materials present a high toxicity against H. coffeaeformis. Pure zinc alginate is also toxic for this strain. However, the addition of calcium in zinc alginate leads to the toxicity reduction. The toxicity of these materials differs according to the strains. Consequently, mixed zinc/calcium alginate are efficient at inhibiting microalgal adhesion with a low level of cells toxicity. These alginate hydrogels are promising materials because they are efficient, cheap, easy to develop and eco-friendly.