In our study, a detailed survey was conducted with the aim to determine the distribution and possible anthropogenic sources of molybdenum in river and stream sediments in the central Upper Silesian Industrial Region (Southern Poland), where for many years, iron and zinc smelters as well as coking and thermal power plants were operating. At the same time, this has also been a residential area with the highest population density in the country. Sediments (1397 samples in total) were collected from rivers and streams, and analysed for the content of molybdenum and 22 other elements. ICP-AES and CV-AAS methods were applied for the determination of the content of elements. The studies revealed molybdenum content in the range of < 0.5–204.8 mg·kg−1 with the average content 1.9 mg·kg−1. About half of the samples contained < 0.5 mg·kg−1 of molybdenum, and only 4.6% of the samples showed values > 5 mg·kg−1. The spatial distribution of molybdenum demonstrated by the geochemical map has indicated that the principal factor determining its content in sediments is the discharge of wastewater from steelworks and their slag heaps. Another source of this element in sediments has been the waste of the historical mining of zinc ore and metallurgy of this metal. Additionally, molybdenum migration from landfills of power plants, coal combustion and Mo emission to the atmosphere and dust fall-out have been significant inputs of Mo pollution to the sediments.