Sampling factors that could affect gas chromatograph (GC) response for volatile analysis such as syringe pumping time, injection volume, needle length, temperature, and the type of volatile were investigated. Capillary GC column segments (steel and glass) were installed in gas-tight syringes and used as needles for volatile analysis. Standard stainless-steel needles were also used. Hexylacetate, ethyl-2-methylbutyrate, 6-methyl-5-hepten-2-one, and butanol standard were measured. The number of pumps required to maximize GC response for each needle–volatile combination was determined. Maximal GC response for hexylacetate using standard stainless steel, capillary glass, and capillary steel needles required 10, 20 and 30 pumps, respectively. However, for butanol measurement, the optimal syringe pump number was 5 to 10 for all needle types. The use of a capillary needle resulted in an increase in GC response in the range of 3- to 15-fold relative to a standard stainless steel needle. Injection volume affected GC response in a needle-and volatile-dependent manner. In no case did injection volume vs. GC response extrapolate through origin. The GC response for capillary column needles increased as temperature decreased. Capillary column needles may be useful tools for analysis of volatiles that readily partition into the column coating.