A method for producing lacto-N-biose I, characterized in that the method comprises causing: (i) a combination of a carbohydrate raw material with an enzyme that catalyzes phosphorolysis of the carbohydrate raw material to give α-glucose-1-phosphate; and (ii) one or more combinations selected from the group consisting of: a combination of UDP-glucose-hexose-1-phosphate uridylyltransferase (EC 2.7.7.12) with UDP-glucose, UDP-galactose, or a mixture thereof; a combination of glucose-1-phosphate uridylyltransferase (EC 2.7.7.9) and galactose-1-phosphate uridylyltransferase (EC 2.7.7.10) with UTP; a combination of glucose-1-phosphate uridylyltransferase (EC 2.7.7.9) and galactose-1-phosphate uridylyltransferase (EC 2.7.7.10) with UDP-glucose and/or UDP-galactose and pyrophosphate; a combination of glucose-1-phosphate uridylyltransferase (EC 2.7.7.9) and galactose-1-phosphate uridylyltransferase (EC 2.7.7.10) with UTP and UDP-glucose and/or UDP-galactose and pyrophosphate; a combination of an enzyme having both activity of glucose-1-phosphate uridylyltransferase and activity of galactose-1-phosphate uridylyltransferase with UTP; a combination of an enzyme having both activity of glucose-1-phosphate uridylyltransferase and activity of galactose-1-phosphate uridylyltransferase with UDP-glucose and/or UDP-galactose and pyrophosphate; and a combination of an enzyme having both activity of glucose-1-phosphate uridylyltransferase and activity of galactose-1-phosphate uridylyltransferase with UTP and UDP-glucose and/or UDP-galactose and pyrophosphate to act in the presence of N-acetylglucosamine, phosphoric acid, lacto-N-biose phosphorylase (EC 2.4.1.211; 1,3β-galactosyl-N-acetylhexosamine phosphlorylase), and UDP-glucose-4-epimerase (EC 5.1.3.2). (i) a combination of a carbohydrate raw material with an enzyme that catalyzes phosphorolysis of the carbohydrate raw material to give α-glucose-1-phosphate; and (ii) one or more combinations selected from the group consisting of: a combination of UDP-glucose-hexose-1-phosphate uridylyltransferase (EC 2.7.7.12) with UDP-glucose, UDP-galactose, or a mixture thereof; a combination of glucose-1-phosphate uridylyltransferase (EC 2.7.7.9) and galactose-1-phosphate uridylyltransferase (EC 2.7.7.10) with UTP; a combination of glucose-1-phosphate uridylyltransferase (EC 2.7.7.9) and galactose-1-phosphate uridylyltransferase (EC 2.7.7.10) with UDP-glucose and/or UDP-galactose and pyrophosphate; a combination of glucose-1-phosphate uridylyltransferase (EC 2.7.7.9) and galactose-1-phosphate uridylyltransferase (EC 2.7.7.10) with UTP and UDP-glucose and/or UDP-galactose and pyrophosphate; a combination of an enzyme having both activity of glucose-1-phosphate uridylyltransferase and activity of galactose-1-phosphate uridylyltransferase with UTP; a combination of an enzyme having both activity of glucose-1-phosphate uridylyltransferase and activity of galactose-1-phosphate uridylyltransferase with UDP-glucose and/or UDP-galactose and pyrophosphate; and a combination of an enzyme having both activity of glucose-1-phosphate uridylyltransferase and activity of galactose-1-phosphate uridylyltransferase with UTP and UDP-glucose and/or UDP-galactose and pyrophosphate