Consumption of appliances in the residential sector in Peru has been growing continuously during the last 20 years. Although social benefits due to this growth are evident, there are also some related environmental impacts in the use and end-of-life (EoL) phases (e.g., inadequate handling or disposal at the EoL stage). Nevertheless, there is also a hidden potential in the growing stock of household appliances, such as their potential exploitation as resources of industrial materials found in urban areas. Thus, the aim of this research paper is to analyze the evolution of the adoption of electronics in Peruvian households and estimate the stock of electrical and electronic equipment and related materials in the residential sector from 2001 to 2019, and greenhouse gases (GHG) emissions due to its use. Material flow analysis is the main methodology used in this research and its application relies on different strategies and the integrated use of official sources. Moreover, a Peruvian input–output table and associated environmental matrices were used to calculate GHG emissions. Results indicate that, in 2019, an average household possessed between 86 and 121 kg of appliances, which means the total stock of household appliances in Peru was in the range of 805,000 to 1,134,000 metric tons, an increase in mass of 70–95% by 2019 compared to 2001. These results will be useful to estimate the urban stock of appliances in the residential sector to help policy-makers design and implement an adequate e-waste management system that comprehends the potential of secondary materials embedded in these products.