Visible and near infrared diffuse reflectance (vis-NIR) spectroscopy is a low-cost, efficient and accurate soil analysis technique and is thus becoming increasingly popular. Soil spectral libraries are commonly constructed as the basis for estimating soil texture and properties. In this study, partial least squares regression was used to develop models to predict the soil organic carbon (SOC) content of 35 soil samples from one field using (i) the Danish soil spectral library (2688 samples), (ii) a spiked spectral library (a combination of 30 samples selected from the local area and the spectral library, 2718 samples) and (iii) three sub-sets selected from the spectral library. In an attempt to improve prediction accuracy, sub-sets of the soil spectral library were made using three different sample selection methods: those geographically closest (84 samples), those with the same landscape and parent material (96 samples) and those with the most alike spectra to spectra from the field investigation (100 samples). These sub-sets were used to develop three calibration models and in predictions of SOC content. The results showed that the geographically closest model, which used the fewest number of samples, gave the lowest root mean square error of prediction ( RMSEP) of 0.19% and the highest ratio of performance to deviation ( RPD) of 3.7, followed by the spiked library, same parent material, the spectral library and the most alike spectra. The spiked library model also gave a low RMSEP value of 0.19% and high RPD value of 3.7% and performed markedly better than the model without spiking, despite using 30 samples for library spiking. The accuracy of the model developed using a sub-set from a spectral library was highly dependent on geographical location, soil parent material and landscape.