We report here the growth and functional properties of silicon-based nanowhisker (NW) diodes produced by the vapor-liquid-solid process using a pulsed laser deposition technique. For the first time, we demonstrate that this method could be employed to control the size and shape of silicon NWs by using a two-component catalyst material (Au/Cu ≈ 60:1). During the NW growth, copper is distributed on the outer surface of the NW, whereas gold sticks as a droplet to its top. The length of NWs is defined by the total amount of copper in the catalyst alloy droplet. The measurements of the electrical transport properties revealed that in contact with the substrate, individual NWs demonstrate typical I-V diode characteristics. Our approach can become an important new tool in the design of novel electronic components.