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In this paper, the nonlinear behavior of coplanar waveguide (CPW) transmission lines fabricated on Si and high-resistivity (HR) Si substrates is thoroughly investigated. Simulations and experimental characterization of 50- Ω CPW lines are analyzed under small- and large-signal operation at 900 MHz for a wide variety of Si substrates with nominal resistivities from 10 Ω-cm up to values higher than 10 kΩ-cm. The introduction of a trap-rich layer to recover the Si substrate nominal HR characteristics is also considered. We experimentally demonstrate that the distortion level of a CPW line lying on Si substrate decreases with the effective resistivity sensed by the coplanar structure. Si substrates of effective resistivity higher than 3 kΩ-cm present harmonic levels below -80 dBm for an output power of +15 dBm.