The atmosphere’s fine articulate Matter (PM2.5) poses various health-related risks. Even though multiple efforts have been made to lower the emissions of these substances, the mortality rate is continuously increasing, requiring immediate inclination of the scientific community towards the design and development of advanced predictive models. Conventional statistical approaches have become dormant due to their limitations in capturing the innate relationships between the pollutants, particularly for predicting PM2.5 concentrations. In contrast, machine and deep learning techniques have shown great potential for forecasting air quality, providing more accuracy than its predecessor techniques. The present study investigates the utilization of hybrid approaches by integrating machine learning models with deep learning models to improve the prediction capabilities of PM2.5 concentration. It uses datasets from the World Air Quality Index (WAQI) and the State of Global Air (SOGA) to analyze the performance of the models on both the daily and annual data, respectively. This ensures the model’s effectiveness on a diversified dataset. The present study implements Random Forest (RF), Polynomial Regression (PR), XGBoost, and Extra Tree Regressor (ETR) coupled with Fully Connected Neural Network (FCNN), Long Short-Term Memory (LSTM), and Bi-directional LSTM (Bi-LSTM) for obtaining optimized results. Finally, after a thorough investigation, the hybrid PR model coupled with FCNN (PR-FCNN) is found to be the best model with improved R-squared (R2) values, portraying its potential for predicting PM2.5 concentration accurately. Based on the experimentation, the preset study recommends implementing hybrid approaches, offering better predictive accuracy in forecasting air pollutants, especially PM2.5.