Development of new greenhouses based on new cultivation methods is one of the most important practical solutions to increase food production in the world. But despite the higher production efficiency of the product, their energy consumption is very high. To solve the energy problem in these greenhouses, the use of renewable energy as a permanent energy source has been suggested by scientists in recent years. Meanwhile, photovoltaics has been investigated by many researchers as a permanent and efficient energy source due to its obvious features, suitability and very good compatibility with agricultural environments and also with greenhouse structures. The results have shown that for the development of photovoltaic covers for greenhouses, in addition to proper photovoltaic efficiency, it is necessary to provide transparency required for the growth of plant in the visible range. One of the technologies that, while having transparency, can be used as a transparent photovoltaic cover for greenhouses, is luminescent solar concentrator (LSC). This photovoltaic device has several components, among which the waveguide is one of the most important components, and its optimization through physical parameters such as geometric factor and refractive index can improve LSC performance. Based on this, in this research, taking into account the parameters of a greenhouse cover and a photovoltaic module, two waveguides made of glass and PMMA were investigated in the construction of LSCs to investigate the effect of the geometric factor and the optical refractive index and their effect on the optical efficiency and the PCE of LSCs was investigated. The results showed that by increasing the thickness of the waveguide from 4 to 6 mm, which reduces the amount of its geometric factor, and also the use of PMMA waveguide in comparison with glass, which in addition to having strength and transparency in the visible region, has a higher refractive index (1.46), can increase the PCE and optical efficiency of LSC from 0.33% to 1% and 0.98% to 4.27%, respectively.