Among the diverse adhesive-bonded joining methods, the co-curing technique offers several advantages for fusing structural components. Co-curing technique effectively enhances specific strengths and ensures more equitable stress distribution. This research investigated the multi-walled carbon nanotubes (MWCNTs) incorporated with varying wt.% in carbon fibre-reinforced polymeric (CFRP) composite joints through co-cure bonding techniques. The effects of flexural and vibration behaviour in CFRP composite joints were evaluated using the three-point bending and free vibration tests. Experimental results revealed that the epoxy adhesive containing 0.5 wt.% nanofiller demonstrated the highest flexural strength and modulus. These values were significantly superior to pure epoxy adhesive, exhibiting increases of 270 and 120%, respectively. However, the 1.0 wt.% of nanofiller exhibited the maximum natural frequency under three vibration modes, which is 29, 17, and 14% higher than the pure epoxy adhesive. The statistical analysis of the results was examined using an ANOVA, ensuring the reliability of the findings. Optimisation and prediction were done with the Levenberg-Marquardt artificial neural network, further reinforcing the confidence in the outcomes. The overall coefficient (R) mean square error of 0.99844 is within the acceptable range, indicating that both outcomes are reliable and in agreement.