Personal care products (PCPs), substances contained in daily hygiene products, become pollutants after being washed away from the human body due to their poor elimination by wastewater treatment plants. Solid-phase microextraction (SPME) has proven to be a reliable sample preparation method for determining contaminants in various matrices. However, commercial SPME fibers’ high price and fragility can hinder their application. Despite novel homemade coatings have been reported in the literature obtaining remarkable results, the elaboration of most of them can be catalogued as complex when the user only desires a low-cost fiber equivalent to a commercial one. This contribution aimed to develop a simple, fast, and low-cost method to produce homemade polydimethylsiloxane fibers with commonly used laboratory equipment and easy-to-acquire materials. These fibers were used to develop and validate a methodology for determining seven PCPs in water by SPME–GC–MS. Homemade fibers were also applied to the analysis of influent and effluent from wastewater treatment plants and surface water samples to demonstrate their usefulness. Homemade fibers achieved equivalent extractions to the commercial ones with a very low cost, making them a suitable alternative.