In this research, the pectin monoliths were prepared via the sol-gel process through different routes of crosslinking and additional freeze-drying. The crosslinking reaction was induced by the use of calcium ions in aqueous solutions and in alcohol/water solutions. The resulting pectin monoliths obtained by freeze-drying were macroporous with open cells, limited specific surface area, moderate mechanical stability and moderate biodegradation rate. The presence of alcohol in crosslinking solution significantly changed the morphology of final pectin monoliths, which was evidenced by the reduction of their pore size for one order. The specific surface area of pectin monoliths obtained through the calcium-water-alcohol route was 25.7 m2/g, the Young compressive modulus was 0.52 MPa, and the biodegradation rate was 45% after 30 days of immersion in compost media. Considering that pectin can be obtained from food waste, and its physical properties could be tailored by different crosslinking routes, the pectin monoliths could find wide application in the pharmaceutical, agricultural, medical and food industries, providing sustainable development concepts.