Biomass burning is an important source of brown carbon (BrC) which poses high-risk threats to human health and the environment. In this study, bio-coal briquette (coal mixed with biomass), a promising solid fuel for residential combustion, is proven to be a clean fuel which can effectively reduce BrC emission. First of all, an orthogonal experiment with three factors and three levels on the physical property of bio-briquette was carried out to identify the optimal preparation conditions including the ratio of biomass to anthracite, particle size and molding pressure. Then a combustion experiment of the bio-coal briquetted was implemented in a simulated residential combustion system. BrC emission factors (EFs) were calculated based on the detected black carbon (BC) concentration by an aethalometer, and other optical characteristics for organic components of extract samplers, such as mass absorption efficiency (MAE) and absorption angstrom index (AAE), were also explored. Lastly, composition analysis of BrC by a gas chromatography (GC) tandem mass spectrometer (MS) and direct visible images by scanning electron microscopy (SEM) were investigated to provide more detail information on BrC EFs and property change. It was shown that bio-coal briquette had such low BrC EFs that 70−81% BrC was reduced in comparison with an interpolation value of 100% biomass and 100% coal. Furthermore, the composition of BrC from bio-coal briquette burning was different, which consisted of more substances with strong wavelength dependence. Consequently, although MAE declined by 60% at a 540 nm wavelength, the AAE value of bio-coal briquette only decreased slightly compared with interpolation values. To be more specific, tar balls, the main existing form of BrC, were distributed much more sparsely in the SEM image of bio-coal briquette. To sum up, a positive reduction effect on BrC was discovered in bio-coal briquette. It is evident that bio-coal briquette can serve as an alternative solid fuel for residential combustion, which is beneficial for both human health and the atmosphere.