Aerogels of natural polysaccharides possess both biocharacteristics of polysaccharides, such as good biological compatibility and cell or enzyme-controlled degradability, and aerogel characteristics, such as very high porosity and specific surface areas that makes them highly attractive in drug delivery. Biodegradable alginate aerogels were synthesized via a sol–gel process. In the present work two methods of ionic cross-linking were used to prepare alginate hydrogels as monoliths and spheres, which can be further easily converted to high surface area aerogels. The aerogels obtained were further used as drug carriers. We investigated the effect of process parameters, such as starting concentration and viscosity of alginate solution, on synthesis products and on model drug (nicotinic acid) release. The results indicate that by using the internal setting cross-linking method for obtaining monolithic aerogels nicotinic acid was released in a more controlled manner. The aerogels thus obtained also exhibited smaller volume shrinkage than the ones described in other publications. However, with increasing alginate concentration in both types of synthesis more compact and cross-linked aerogels were formed.