Electrospinning is a robust technique for producing micro/nano-scale fibrous structures, influenced by intricate interplays of fluid dynamics, aerodynamics, and electromagnetic forces. Depending on the desired outcome, these fibers can adopt various morphologies, including solid, tubular, concentric, and gradient. Such morphologies are modulated by parameters such as collector configuration, flow rate, voltage, solution properties, and nozzle dimensions. However, the task of modeling and predicting these multifaceted morphologies remains complex. Aligned microfibers with 3D orientation hold promise in tissue engineering, regenerative medicine, and drug delivery, necessitating meticulous control over the fabrication parameters. In our research, we tapped into machine learning (ML) to address these challenges. Classification ML models were designed to predict fibrous patterns—aligned, random, or jet branching—based on determinants like voltage, flow rate, and collector configurations. Notably, the Random Forest (RF) and Support Vector Machine (SVM) models, especially with radial kernel-trick, displayed outstanding predictive capabilities on the test data. Furthermore, regression-based ML was harnessed to discern fiber alignment coherency and inter-fiber distances. Models such as Lasso and Ridge regression elucidated predictive coefficients for these characteristics, while ensemble models, like gradient-boosting (GB) decision trees (DT), showcased prowess in regression scenarios. Key findings spotlighted the significance of parameters like plate gap for alignment coherency and needle-to-collector distance for inter-fiber spacing. As we strive to gain granular control over micro/nano feature morphology in electrospinning, understanding predictor-response dynamics is imperative. Our investigation underscores the essential role of ML in enhancing both qualitative and quantitative precision in fabricating advanced fibrous structures. Moreover, fusing ML with real-time process monitoring offers groundbreaking potential, particularly in Bio-Fabrication, regenerative medicine, and tissue engineering, where high-precision manufacturing remains a top priority.