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Early detection of breast cancer reduces the risk of death. In this investigation, the main goal is to explore the ability of near-field microwave techniques to detect tumors inside the breast using open-ended rectangular waveguide probes. The interaction of electromagnetic waves radiated from a rectangular waveguide into a multilayer structure is studied. Knowing the behavior of microwaves radiated from the waveguide, the phase and/or magnitude variations of the reflection coefficient at the waveguide aperture due to the presence of a tumor are calculated. Consequently, detection of a tumor can be attained. Various measurement optimization parameters are exploited to maximize the variations of the reflection coefficient. Results detailing the process of arriving at optimal measurement parameters are revealed and discussed to demonstrate the potential of such technique.