The work aims to develop a rapid electrochemical determination method of pentachlorophenol (PCP) in cigarette paper. Based on the same unit cell parameters and isomorphism of ZIF-8 and ZIF-67, the three-dimensional nanoporous carbon (NGPC) was prepared with ZIF-8@ZIF-67 as a template. Considering the advantage of the large specific surface area and high electron transfer efficiency of NGPC, the constructed sensor (named NGPC/SPCE) had a good response to PCP. At the detection potential of 0.86 V, the sensor had a high sensitivity (2.452 µA.cm−2.L.mg−1) with good selectivity. Besides, the sensor possessed good accuracy and precision for detection of PCP. The recovery results of the three concentration gradients were between 95.7%-98.6%. Additionally, the relative standard deviation of the six consecutive test results was 2.07%. The sensor had good long-term stability for detection of PCP. After 25 days of continuous detection, the sensor can still maintain 88.1% of the initial sensitivity. Thus, the sensor developed in the work is suitable for detection of PCP in cigarette paper with a satisfactory result.