Adding natural biomass to poly(lactic acid) (PLA) as a reinforcing filler is a way to change the properties of PLA. This paper is about preparing PLA/biomass composites by physically melting and blending Chinese Spirits distiller’s grains (CSDG) biomass and PLA to optimize the composite performance. Composites of modified PLA (MPLA) with varying amounts of CSDG were also prepared by the melt-mixing method, and unmodified PLA/CSDG composites were used as a control group for comparative analysis. The functional groups of MPLA enhanced the compatibility between the polymer substrate and CSDG. The composite water vapor/oxygen barrier and mechanical properties were studied. It was found that the barrier and mechanical properties of MPLA/CSDG composites were significantly improved. SEM was adopted to examine the tensile section structure of the composites, and the compatibility between the filler and the matrix was analyzed. An appropriate amount of CSDG had a better dispersibility in the matrix, and it further improved the interfacial bonding force, which in turn improved the composite mechanical properties. X-ray diffraction, thermogravimetric analysis, and differential scanning calorimetry were conducted to determine the crystalline properties and to analyze the stability of the composites. It was found that the CSDG content had a significant effect on the crystallinity. Barrier and biodegradation mechanisms were also discussed.