We have studied the intermolecular complex formation between trifluoromethoxybenzene and methanol (CD₃OD) in superfluid helium droplets by infrared spectroscopy in the spectral range of 2630–2730 cm⁻¹, covering the O–D stretches of methanol-d₄ (CD₃OD). The cluster size associated with the observed bands is deduced from the variation of infrared intensity of a particular band with the partial pressures of trifluoromethoxybenzene and methanol. Quantum chemical calculations are performed at the MP2/6-311++G(d,p) level of theory to complement the experimental results. As a result, we have identified six different conformers of the trifluoromethoxybenzene⋯methanol intermolecular complex: three bound via O–H⋯O hydrogen bonds and the other three via O–H⋯π hydrogen bonds. Furthermore, to access the effect of fluorination on the methyl unit of anisole molecules, we compare the IR spectrum of trifluoromethoxybenzene (C₆H₅OCF₃)⋯methanol with our earlier reported spectrum of anisole (C₆H₅OCH₃)⋯methanol.