Natural fiber-based polymer composites have greater advantages due to their superior mechanical properties and environmentally friendly nature. In the present study, pineapple leaf (PALF) and roselle fiber (RSF) reinforced vinyl ester hybrid composites were fabricated by the hot compression molding method, and their physical properties, mechanical properties, water absorption rate, and tribological behavior were investigated and analyzed. This research investigation has been conducted to reveal a significant hybrid of natural fiber reinforced polymer composites for commercial engineering applications. Mechanical properties were examined for their tensile, flexural, compression, hardness, and impact properties. Moreover, the fractured surfaces of the tensile specimen were analyzed using a scanning electron microscope. Water absorption behaviors were then accomplished by immersing the composite samples in standard distilled water and analyzing the water penetration percentage. The tribological behavior was simply studied by using a pin-on-disc tribometer apparatus to evaluate the specific wear rate and coefficient of friction. From the results, it was concluded that the hybrid composites provided higher results in all kinds of formats when compared with single-fiber composites. Among the hybrid composites, the 24PALF/16RSF/60VE sample was particularly promising for its improvement in mechanical properties of 103.9% tensile strength, 109.7% flexural, 26.2% compression, 56.9% impact, and 113.5% hardness compared to the neat resin sample. Thus, the results illustrate that the hybridization of PALF and RSF fibers with a vinyl ester matrix generates enhanced mechanical behaviors, which indeed make it desirable for use in non-structural electrical and electronics insulation board and component applications.