In this paper, we report on the impact of metal/polymer interfaces on the rectifying behavior of novel multi-segmented hybrid nanowires (HNWs) made of metallic and conjugated polymer (CP) segments. Using HNWs integrated in micromachined devices, the relationship between electronic properties and original structure is revealed. By combining transmission electron microscopy (TEM) and current-voltage (I-V) spectroscopy studies performed on several symmetric and asymmetric HNWs structures, we show that rectifying I-V characteristics are observed only for asymmetric HNWs. Moreover, it is shown that the rectification ratio can be improved up to 3 orders of magnitude by a proper selection of the HNW composition. While the rectifying behavior is observed in HNWs after oxidative or acid doping, the charge transport mechanism in as-synthesized HNWs is bulk-limited and independent from their structure. Both symmetric and asymmetric HNWs exhibit Ohmic and non-linear I-V curves above and below T~120 K, respectively. These electrical behaviors are consistent with a smooth transition from an Ohmic to a non-Ohmic variable-range-hopping (VRH) mechanism. We discuss the origin of these nonlinearities comparing the two- and four-probe measurements on single HNWs and we propose a simple model based on dual back-to-back Schottky diodes to explain qualitatively the rectifying properties.