A process of producing C1-C4 alkyl nitrite, comprising the following steps: a) firstly feeding nitrogen oxide and oxygen into Reactor I, contacting with an aluminosilicate catalyst, and reacting to produce an effluent I containing NO2 and unreacted NO; b) feeding the effluent I and C1-C4 alkanol into Reactor II, and reacting to produce an effluent II containing C1-C4 alkyl nitrite; and c) separating the effluent II containing C1-C4 alkyl nitrite to obtain C1-C4 alkyl nitrite; wherein reactor I is a fixed bed reactor, and Reactor II is a rotating high-gravity reactor; said nitrogen oxide in step a) is NO, or a mixed gas containing NO and one or more of N2O3 and NO2, wherein the molar number of NO is greater than that of NO2, if any; and the molar ratio of NO in nitrogen oxide to oxygen is 4-25:1.