The ultra-wide band (UWB) technology has many advantages in positioning and measuring systems; however, powers of UWB signals rapidly reduce while traveling in propagation environments, hence detecting UWB signals are difficult. Various modulation techniques are applied for UWB signals to increase the ability for detecting the reflected signal from transmission mediums, such as pulse amplitude modulation (PAM), pulse position modulation (PPM), and so on. In this paper, we propose an ultra-wide band pulse position modulation technique with optimized additional time shift (UWB-PPM-ATS) to enhance the accuracy in locating buried object in nondestructive environments. Moreover, the Levenberg–Marquardt Fletcher algorithm (LMFA) is applied to determine the medium parameters and buried object location simultaneously. The influences of proposed modulation technique on determining system’s parameters, such as a propagation time, distance, and properties of the medium are analyzed. Calculation results indicate that the proposed UWB-PPM-ATS gives higher accuracy than the conventional one such as UWB-OOK and UWB-PPM in both homogeneous and heterogeneous environments. Furthermore, the LMFA with the proposed UWB-PPM-ATS outperforms the LMFA with the traditional modulation method, especially for unknown propagation environment.