A movable probe that fiber couples both the beam delivery and the signal collection functions of gas-phase laser-induced breakdown spectroscopy (LIBS) measurements was evaluated. The adjustable probe was used to investigate the effect of delivery fiber curvature on plasma characteristics and the associated effect on LIBS spectra and to further identify issues remaining to facilitate fully fiber-coupled gas-phase LIBS measurements. LIBS data were collected from lean methane–air mixtures of various equivalence ratios and spectroscopically analyzed to establish the ability to determine relative fuel–air ratio. Measurements with straight delivery fiber were compared to those with the fiber curved at specific radii. Decreasing fiber radius of curvature decreased fiber transmission efficiency and reduced the spark formation probability by almost a factor of 2. For constant fiber input energy, this decreased transmission increased the percentage of failed spark formations and influenced the LIBS elemental ratio calculations. However, minimal difference was found between LIBS measurements with straight or curved fiber as long as the output energy and a constant laser beam spot diameter were maintained on the exit beam focusing lens. A significant reduction in data scatter and improved linearity were achieved by using the Balmer series ${\mathrm{H}}_{\alpha }$ and ${\mathrm{H}}_{\beta }$ hydrogen emission line ratio as a data selection criterion. Observed linear variation of $\mathrm{H}/\mathrm{N}$ elemental ratio with equivalence ratio confirmed the possibility of a flexible, light-contained, fully fiber-coupled probe for remote gas-phase LIBS analysis.