A cost effective solution assembly method has been explored for preparing zinc(II)1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexa-decafluoro-29H,31H-phthalocyanine/multi-walled carbon nanotubes (F₁₆ZnPc/MWCNTs-COOH) hybrid. Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, transmission electron microscopy (TEM) and field emission scanning electron microscopy (FE-SEM) investigations confirm the non-covalent anchoring of F₁₆ZnPc onto MWCNTs-COOH through п-п stacking interactions. Further, a highly sensitive and selective chemiresistive Cl₂ sensor has been fabricated using F₁₆ZnPc/MWCNTs-COOH hybrid. The response of sensor is found to be 21.28% for 2 ppm of Cl₂ with a response time of 14 s and theoretical detection limit of the sensor is found down to 0.06 ppb. The improved Cl₂ sensing characteristics of hybrid are found to be originated from the synergetic interaction between F₁₆ZnPc and MWCNTs-COOH. The underlying mechanism for improved gas sensing performance of F₁₆ZnPc/MWCNTs-COOH sensor towards Cl₂ has been explained using Raman, X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS) studies.