This study addresses the issue of alternative pathways for breeding plutonium in a 900 MWe three loop thermal pressurized water reactor (PWR), either fueled with uranium fuel (3.5% U-235) or with mixed fuel (20% MOX). During the operation of a nuclear reactor the in-core neutron flux and the ex-core neutron flux are monitored with flux detectors. At the places where those detectors operate, the guide thimbles and the vessel wall, respectively, the neutron flux can be used to irradiate material samples. This paper investigates whether it would be possible to produce plutonium by breeding it at the walls of a PWR vessel and/or in the guide thimbles. The neutron flux in the reactor and the corresponding multi-group spectra are estimated with Monte Carlo simulations for different positions at the vessel wall of a PWR operating with either UO2 or MOX. Then the irradiation of fresh uranium samples at the vessel wall and in the guide thimbles are calculated and the isotopic composition of the irradiated samples are determined. The minimum irradiation period and the necessary minimum amount of fresh uranium to breed different grades of plutonium are derived.