Embedded optical fibre sensors (OFSs) offer the potential to monitor the internal strains at various stages during the manufacturing and service life of fibre-reinforced polymer (FRP) composite structures. Various aspects associated with the embedment of OFSs, such as integration, material compatibility, and sensing performance of the embedded sensor needs to be investigated to develop reliable OFSs based internal sensing platform for composite structures. In this study, Polyimide (PI) and Polyether ether ketone (PEEK) coated optical fibres (OF) were embedded into glass fibre-reinforced polymer (GFRP) composites to evaluate four important aspects associated with the embedment of OFs, which include; i). Structural integrity of the OFs against chemical reactions from vinyl ester resin and its additives through immersion testing, ii). Methods of integrating the OFs into layered glass fibres for the vacuum resin infusion manufacturing process, iii). Sensing performance of the embedded OFs during manufacturing and structural testing (tensile and compressive), and iv). Internal structural integrity of the embedded OFs and the host composite structure using X-Ray micro-computerised tomography technique (μ-CT). The results from the immersion testing and manufacturing process monitoring showed that both PEEK and PI coated OFs can resist the chemical and mechanical stresses caused by resin polymerisation during curing process. The subsequent mechanical testing showed a similar sensing performance by the PI and PEEK coated OFs. Under tensile loads, the OFs monitored the tensile strain distribution up to 7,000 με and compressive strain distribution up to −1,200 με under flexural loading without compromising their optical performance. Finally, the μ-CT scanning results had shown a minimal structural deterioration of the embedded OFs and host composite structure. The outcomes from this detailed experimental investigation on the embedment of OFS in GFRP structures provided useful information towards the integration and performance of optical sensors in composite structures.