: This research investigates an effective alkali (NaOH) treatment and fire-retardant coating to produce biocomposites from frost-retted hemp fiber and PLA. The fiber surface treatment with various NaOH concentrations was investigated throughout a range of soaking times. The results show that the extracted non-cellulosic fiber content increases with treatment duration and NaOH concentration, while the fraction of targeted components removed remains nearly unchanged after soaking for 1, 2, and 4 h with a 5 wt.% NaOH solution. At the composite level, the treatment with 5 wt.% NaOH solution for 1 h emerged as the most efficient, with tensile strength, Young’s modulus, flexural strength, and flexural modulus of 89.6 MPa, 9.1 GPa, 121.6 MPa, and 9.6 GPa, respectively, using 30 wt.% fibrous reinforcement. The fire performance of the examined batches of biocomposites improved significantly with the novel fire-retardant (Palonot F1) coating. However, the tensile strength notably decreased, while the flexural properties showed only a slight reduction. In most cases, the biocomposites with the alkali-treated hemp fiber had delayed ignition during the 5 min exposure to the cone heater. The findings in this work contribute to studies that will be required to give design guidelines for sustainable building options.