Approaches for accurate neural network training for library-based critical dimension (CD) metrology are described. Approaches for fast neural network training for library-based CD metrology are also described. In an example, a method includes optimizing a threshold for a principal component analysis (PCA) of a spectrum data set to provide a principal component (PC) value, estimating a training target for one or more neural networks, training the one or more neural networks based both on the training target and on the PC value provided from optimizing the threshold for the PCA, and providing a spectral library based on the one or more trained neural networks.