Alginic acid, a widely used naturally occurring carbohydrate which is generally derived from brown seaweeds, can be considered as a bifunctional heterogeneous and green biopolymeric organocatalyst. Alginic acid, without any post-modification with active Bronsted or Lewis acid centers, was found to be a highly active, cost-effective, commercially-available, renewable and recoverable heterogeneous biopolymeric organocatalyst for the expeditious synthesis of polyhydroquinolines (PHQs). Polyhydroquinolines were synthesized from the four-component Hantzsch reaction of ethyl acetoacetate, different aldehydes, ammonium acetate and cyclic 1,3-diones under mild conditions in high to quantitative yields, 75-97%, using alginic acid. Furthermore, alginic acid was found to be reusable for at least 6 consecutive cycles without considerable loss of its catalytic activity.