Emissions from small-scale heating appliances significantly contribute to exacerbating Serbia’s severe air quality challenges. This study investigates two types of pellets, produced from wheat crop residue and a mixture of wheat and rapeseed, as potential alternatives to wood pellets. The analysis covers key solid biofuel characteristics, including heating value, moisture, volatile matter, elemental composition, ash content, and melting temperature, in accordance with normative specifications. Results reveal that agropellets from wheat and the mixture fail to meet established requirements, disqualifying them from any ENplus classification. Emission characteristic tests, conducted in an automatic residential pellet stove, measure O2, CO2, CO, NOx, SO2, and TOC. Comparative analysis with wood pellets quantitatively indicates higher gaseous pollutant emissions from agropellets. Notably, the combustion of agropellets proves unsuccessful, leading to the extinguishing of the fire in the appliance, rendering them unsuitable for household use. The findings underscore the importance of ensuring high-quality pellets are available on the market and in domestic appliances, presenting implications for end-users and policymakers. Addressing these issues is crucial for mitigating air quality concerns and further study associated with heating in households.