Nanowires represent a promising class of materials for exploring new concepts in solar energy conversion. Here we report the first experimental realization of axial modulation-doped p-i-n and tandem p-i-n(+) -p(+)-i-n silicon nanowire (SiNW) photovoltaic elements. Scanning electron microscopy images of selectively etched nanowires demonstrate excellent synthetic control over doping and lengths of distinct regions in the diode structures. Current-voltage (I-V) characteristics reveal clear and reproducible diode characteristics for the p-i-n and p-n SiNW devices. Under simulated one-sun solar conditions (AM 1.5G), optimized p-i-n SiNW devices exhibited an open circuit voltage (Voc) of 0.29 V, a maximum short-circuit current density of 3.5 mA/cm(2), and a maximum efficiency of 0.5%. The response of the short-circuit current versus Voc under varying illumination intensities shows that the diode quality factor is improved from n=1.78 to n=1.28 by insertion of the i-type SiNW segment. The temperature dependence of Voc scales as -2.97 mV/K and extrapolates to the crystalline Si band gap at 0 K, which is in excellent agreement with bulk properties. Finally, a novel single SiNW tandem solar cell consisting of synthetic integration of two photovoltaic elements with an overall p-i-n(+) -p(+)-i-n structure was prepared and shown to exhibit a Voc that is on average 57% larger than that of the single p-i-n device. Fundamental studies of such well-defined nanowire photovoltaics will enable their intrinsic performance limits to be defined.