The electrical transport properties of amorphous CNx/p‐Si heterostructures fabricated using reactive facing‐target sputtering were investigated systematically. The obvious rectifying effect is observed in the I–V curves for the heterostructures fabricated at the nitrogen partial pressure ($P_{{\rm N}_2 }$) of 20%, and the resistance of the heterostructures in both the forward and reverse voltage ranges increases with the decrease of the current and temperature. At low‐voltage range, the resistance satisfies the relation of ${\rm log}\,R \propto {\rm log}\,I$, and the slope of the ${\rm log}\,R \propto {\rm log}\,I$ plots increases with the decrease of temperature. The electrical transport characteristic of the heterostructures can be affected by the changes of the number and cluster size of sp2 C and the ratio of N–C(sp2)/N–C(sp3) by adjusting $P_{{\rm N}_2 }$ significantly, and the good rectifying effect of the heterostructures fabricated at a certain condition makes them useful in the field of electronic devices.