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In a synthesis of urea using ammonia in a highly excessive molar ration, unreacted materials are decomposed and separated by subjecting the urea synthesis effluent to a stripping step using carbon dioxide at a pressure equal to the urea synthesis pressure. The thus-separated gaseous mixture of ammonia and carbon dioxide is condensed through an indirect heat exchange with an effluent stream discharged from the stripping step and lowered to a pre-determined pressure level. Resulting condensation heat is used for the decomposition and separation of unreacted materials still remaining in said effluent stream. By choosing suitable operation conditions for each step of the present invention, it is possible to reduce the amount of high pressure steam to be required and to minimize the amount of low pressure steam to be recovered.