Progressive and increasingly noticeable climate change is forcing the search for new energy sources to reduce greenhouse gas emissions, especially carbon dioxide. One way to reduce greenhouse gas emissions is by gradually replacing fossil fuels with biofuels. The authors of this work addressed the production of second-generation biofuel. The purpose of this study was to produce second-generation biodiesel from babassu palm oil (BBuE) and first-generation biodiesel from rapeseed oil (RME), to study their properties, and to determine the effect of the addition of these biodiesels to diesel fuel on selected properties of “B” fuels that affect the fuel–air mixture formation process and the combustion process. Biodiesel from babassu oil was produced because it is non-edible and has a different composition than canola oil. Then, fuels were prepared that were mixtures of diesel oil and biodiesel containing from 10 to 40% (v/v) BBuE or RME (B10, B20, B30, and B40).Tests were conducted on selected physicochemical properties of the obtained fuels. “B” fuels prepared with BBuE and DF were shown to have more favorable fuel properties than those obtained from RME and DF. Fuels that are blends of BBuE and DF have slightly higher heating values, higher cetane number values, a more favorable distillation curve, lower dynamic viscosity values as a function of temperature, and marginally lower flash point values compared to the corresponding blends of RME and DF. Esters with shorter molecules have been shown to have more favorable fuel properties.