In clinical practice, the catheter has to be placed at an accurate position during anesthesia administration. However, effectively guiding the catheter to the accurate position in deeper tissues can be difficult for an inexperienced practitioner. We aimed to address the current issues associated with catheter placement using a novel smart assistance system for blood vessel catheter placement. We used a hollow introducer needle embedded with dual wavelength (690 and 850 nm) optical fibers to advance the tip into the subclavian vessels in anesthetized piglets. The results showed average optical density changes, and the difference between the absorption spectra and hemoglobin concentrations of different tissue components effectively identified different tissues (p < 0.05). The radial basis function neural network (RBFNN) technique was applied to distinguish tissue components (the F-measure value and accuracy were 93.02% and 94%, respectively). Finally, animal experiments were designed to validate the performance of the proposed system. Using this system based on oximetry, we easily navigated the needle tip to the target vessel. Based on the experimental results, the proposed system could effectively distinguish different tissue layers of the animals.