Piezoelectric polymer composites, particularly polyvinylidene fluoride (PVDF) blended with barium titanate (BT), show promise for wearable technologies as both energy harvesters and haptic actuators. However, these composites typically exhibit limited electromechanical coupling and insufficient β-phase formation. This study presents a novel approach using ionic liquids (ILs) to enhance PVDF-based piezoelectric composite performance. Through solution-casting methods, we examined the effect of IL concentration on the structural, mechanical, and piezoelectric properties of PVDF/BT composites. Results demonstrate that the use of IL significantly improves β-phase crystallization in PVDF while enhancing electrical properties and mechanical flexibility, which are key requirements for effective energy harvesting and haptic feedback applications. The optimized composites show a 25% increase in β-phase content, enhanced flexibility, and a 100% improvement in piezoelectric voltage output compared to other more conventional PVDF/BT systems. The IL-modified composite exhibits superior piezoelectric response, generating an output voltage of 9 V and an output power of 40.1 µW under mechanical excitation and a displacement of 138 nm when subjected to 13 V peak-to-peak voltage, making it particularly suitable for haptic interfaces. These findings establish a pathway toward high-performance, flexible piezoelectric materials for multifunctional wearable applications in human–machine interfaces.