The present work proposes a novel method to improve the calibration accuracy of laser-induced breakdown spectroscopy (LIBS) in high-pressure combustion environments. Typically, optical plasma breakdown suffers from instability in highly pressurized environments, and the plasma emits photons of noisy and broadened spectra that are unusable for extracting quantitative property information. An improved plasma emission spectrum signal is obtained by modulating or chopping the pulse width of a fundamental 10 Hz Nd:YAG laser pulse by limiting the stochastic inverse-Bremsstrahlung (IB) photon absorption process. The modulated pulse duration is decreased from 9.2 ns to 5 ns utilizing a simple optical setup prior to being focused into a high-pressure combustor. In order to evaluate the impact of the modulated temporal laser pulse profile on the plasma emission, Proper Orthogonal Decomposition (POD) is applied to the emission spectra collected over a customized flat flame burner with varied composition and pressure. POD is capable of decomposing property-sensitive spectrum components that determine the accuracy of the spectrum calibration for property measurements using LIBS. The POD-analyzed database comprises 50 flame cases with pressure and equivalence ratios ranging from 1 to 10 bars and 0.7 to 1.1, respectively. Two Reduced-Order Models (ROMs) are trained with the collected spectra; modulated and original pulse, to predict three distinct flame properties; pressure, equivalence ratio, and adiabatic flame temperature. The output model estimates pressure, equivalence ratio and adiabatic flame temperature with an improved accuracy of 8%, 7% and 55%, respectively when the ROM is trained with chopped spectra over the calibrated pressure range. This is because the reduced pulse width in general lowers the signal level of broadband plasma emission that is sensitive to pressure. The POD-aided spectrum analyses suggest that flexible pulse modulation helps to improve the calibration accuracy in a broad gas density range with varied pressure and temperature.