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The availability of position information is of great importance in many commercial, public safety, and military applications. The coming years will see the emergence of location-aware networks with submeter accuracy, relying on accurate range measurements provided by wide bandwidth transmissions. In this two-part paper, we determine the fundamental limits of localization accuracy of wideband wireless networks in harsh multipath environments. We first develop a general framework to characterize the localization accuracy of a given node here and then extend our analysis to cooperative location-aware networks in Part II. In this paper, we characterize localization accuracy in terms of a performance measure called the squared position error bound (SPEB), and introduce the notion of equivalent Fisher information (EFI) to derive the SPEB in a succinct expression. This methodology provides insights into the essence of the localization problem by unifying localization information from individual anchors and that from a priori knowledge of the agent's position in a canonical form. Our analysis begins with the received waveforms themselves rather than utilizing only the signal metrics extracted from these waveforms, such as time-of-arrival and received signal strength. Hence, our framework exploits all the information inherent in the received waveforms, and the resulting SPEB serves as a fundamental limit of localization accuracy.