Room temperature ionic liquids (ILs) are well established stationary phases (SPs) for gas chromatography (GC) in several fields of applications because of their unique and tunable selectivity, low vapor pressure and volatility, high thermal stability (over 300°C), and good chromatographic properties. This study is focused on an IL based on a phosphonium derivative (trihexyl(tetradecyl)phosphonium chloride, [P66614+] [Cl−]), previously shown to be suitable as a gas chromatographic SP because of its unique selectivity. In particular, it aims to establish the operative conditions to apply [P66614+][Cl−] to routine analysis of samples containing medium to high volatility analytes with different polarity, organic functional groups and chemical structure. In the first part, the study critically evaluates long term [P66614+][Cl−] column stability and maximum allowable operating temperatures (MAOT). The relatively low MAOT (210°C) requires the adoption of a dedicated approach for analytes eluting above this temperature based on a suitable combination of efficiency and selectivity, and column characteristics (length, inner diameter and film thickness) and operative conditions. The performance of [P66614+][Cl−] as a GC SP have been validated through the Grob test, a model mixture of 41 compounds of different polarity, structure, and with different organic functional groups in the flavor and fragrance field, a standard mixture of 37 fatty acid methyl esters, some essential oils containing pairs or groups of compounds of different volatility critical to separate in particular peppermint, thyme, oregano, sandalwood and frankincense. The above approach has produced highly satisfactory separations with all of the samples investigated.