A simple and effective approach for highly selective preparation of nitrocyclohexane from cyclohexane using tert-butyl nitrite as a nitrating agent under atmospheric pressure has been successfully developed in this work. The results indicate that the N-hydroxyphthalimide catalyst gave the best results with 27.3 % of cyclohexane conversion and 88.0 % of selectivity to nitrocyclohexane under optimal reaction conditions. The present reaction provides a novel strategy for the synthesis of nitroalkanes from the nitration of low-carbon alkanes because of the mild reaction condition, simple experimental procedure and high selectivity towards the desired product. This method may be very significant to establish such a synthesis method for aliphatic nitro-compounds from the low-carbon alkanes in organic fields.