In this paper, a novel hybrid Maximum Power Point Tracking (MPPT) algorithm using Particle-Swarm-Optimization-trained machine learning and Flying Squirrel Search Optimization (PSO_ML-FSSO) has been proposed to obtain the optimal efficiency for solar PV systems. The proposed algorithm was compared with other well-known methods viz. Perturb & Observer (P&O), Incremental Conductance (INC), Particle Swarm Optimization (PSO), Cuckoo Search Optimization (CSO), Flower Pollen Algorithm (FPA), Gray Wolf Optimization (GWO), Neural-Network-trained Machine Learning (NN_ML), Genetic Algorithm (GA), and PSO-trained Machine Learning. The proposed algorithm was modelled in the MATLAB/Simulink environment under different operating conditions, for example, with step changes in temperature, solar irradiance, and partial shading. The proposed algorithm improved the efficiency up to 0.72% and reduced the settling time up to 76.4%. The findings of the research highlight that PSO_ML-FSSO is a potential approach that outperforms all other well-known algorithms tested herein for solar PV systems.