Recent studies have shown that satellite communication (SatCom) will have a fundamental role in the next generation non-terrestrial networks (NTN). In SatCom, radio frequency (RF) or free-space optical (FSO) communications can be used depending on the communication environment. Motivated by the complementary nature of RF and FSO communication, we propose a hybrid RF/FSO transmission strategy for SatCom, where the satellite selects RF or FSO links depending on the weather conditions obtained from sensors and used for the context-awareness. To quantify the performance of the proposed network, we derive the outage probability (OP) expressions by considering different weather conditions. Moreover, asymptotic analysis is conducted to obtain the diversity order. Furthermore, we investigate the impact of non-zero boresight pointing errors and illustrate the benefits of the aperture averaging to mitigate the effect of misalignment and atmospheric turbulence. Finally, we suggest effective design guidelines that can be useful for system designers. The results have shown that the proposed strategy performs better than the dual-mode conventional hybrid RF/FSO communication in terms of OP offering some power gain.