Portland cement-based composites were prepared with coffee exocarp (pretreated with water or NaOH) via vacuum extraction technology. An orthogonal test was adopted to analyze the influence of various factors on mechanical properties of the composite. The morphology and composition of the pretreated coffee exocarp and composites were analyzed via environmental scanning electron microscopy and X-ray diffraction, respectively. The results showed that the coffee exocarp content and vacuum extraction time significantly affected the compressive strength. An addition of 10% coffee exocarp had a slight negative effect on the mechanical properties but enhanced the crack inhibition and overall toughness of the composite. The scanning electron microscopy and X-ray diffraction results showed that the composite containing coffee exocarp pretreated with 4% NaOH solution had the highest density and exhibited the best properties due to mechanical interlocking between the coffee exocarp and cement. After 28 d of curing, the composites exhibited a maximum compressive strength of 15.72 MPa, a mass that was approximately 37% less than that of ordinary Portland cement samples, and a bulk density of 1.5 g/cm3 to 1.6 g/cm3. Hence, the produced biocomposites could be used for low-load pavements, providing a new type of economical building material.