Generally, articular cartilage disorder at the junction mainly results from constantly repeated dynamic tension/compression effects with aging time. Piezoelectric materials can deliver variable electric signals analogous to native tissues such as bone and cartilage associated with extracellular matrix (ECM) materials. Thus, there is a high need of degradable piezoelectric scaffold, which mimics the dynamic mechanical loading and optimizes the chondrocyte differentiation during the degradation. A degradable aligned electrospun poly-L-lactic acid (PLLA) modified with rGO and PDA fibrous scaffolds with different orientations and surface morphologies (wrinkled and porous) was developed as a biocompatible and degradable piezoelectric scaffold with the self-powered tunable piezoelectricity to modulate cell behavior and cell differentiation of ATDC5 cells by tuning the degradation effect. The electrical output and mechanical properties of the composite fibrous scaffold can be improved by adding rGO and applying mechanical force along the 90° orientation. With changing the degradation behavior, dynamic mechanical loading on the porous PLLA/rGO/PDA fibrous scaffold exhibits significant increase in cell proliferation and secretion of extracellular matrix (ECM). More surprisingly, long-term degradation favored to promote cell differentiation of ATDC5 towards a chondrogenic phenotype due to dynamic mechanical loading, low-intensity electrical stimulation and interconnected porous structural morphology. In contrast, on the wrinkled PLLA/rGO/PDA fiber inducing mineralization with the differentiation of ATDC5 into osteocytes. The modulation of the degraded environment and electrical stimulation of the piezoelectric scaffold offers an effective alternative to influence cell functions, significantly improving the ECM secretion and cell differentiation.