This study focuses on the assessment of surface solar radiation (SSR) based on operational neural network (NN) and multi-regression function (MRF) modelling techniques that produce instantaneous (in less than 1 min) outputs. Using real-time cloud and aerosol optical properties inputs from the Spinning Enhanced Visible and Infrared Imager (SEVIRI) on board the Meteosat Second Generation (MSG) satellite and the Copernicus Atmosphere Monitoring Service (CAMS), respectively, these models are capable of calculating SSR in high resolution (1 nm, 0.05°, 15 min) that can be used for spectrally integrated irradiance maps, databases and various applications related to energy exploitation. The real-time models are validated against groundbased measurements of the Baseline Surface Radiation Network (BSRN) in a temporal range varying from 15 min to monthly means, while a sensitivity analysis of the cloud and aerosol effects on SSR is performed to ensure reliability under different sky and climatological conditions. The simulated outputs, compared to their common training dataset created by the radiative transfer model (RTM) libRadtran, showed median error values in the range -15 to 15% for the NN that produces spectral irradiances (NNS), 5-6% underestimation for the integrated NN and close to zero errors for the MRF technique. The verification against BSRN revealed that the real-time calculation uncertainty ranges from -100 to 40 and -20 to 20Wm-2, for the 15 min and monthly mean global horizontal irradiance (GHI) averages, respectively, while the accuracy of the input parameters, in terms of aerosol and cloud optical thickness (AOD and COT), and their impact on GHI, was of the order of 10% as compared to the ground-based measurements. The proposed system aims to be utilized through studies and real-time applications which are related to solar energy production planning and use.