A series of VPO composites were employed to catalyze the reaction of cyclohexane with nitrosyl sulfuric acid in the presence of fuming sulfuric acid. To our delight, epsilon-caprolactam was for the first time directly obtained through such one-step catalytic process. VPO composite catalysts were proven to be efficient for the reaction, especially, the transition metals introduced to Al-VPO composite catalysts could improve the reactions selectivity to some extent. Among them, the Mn-Al-VPO composite catalyst gave the best results with 11.65% of conversion and 34.70% of selectivity to epsilon-caprolactam. While the conversion and selectivity are too low at this time to be commercially viable, this discovery establishes a potential new single step process for making epsilon-caprolactam from cyclohexane. A reaction mechanism is proposed.