Visible (Vis) and near infrared (NIR) reflectance spectroscopy is a rapid and non-destructive technique that has found many applications in assessing the quality of agricultural commodities, including wool. In this study, Vis and NIR spectroscopy combined with multivariate data analysis was investigated regarding its feasibility in predicting a range of fibre characteristics in raw alpaca wool samples. Mid-side samples (n = 149) were taken from alpacas from a range of colours and ages at shearing time over 4 years (2000 to 2004) and subsequently analysed for fibre characteristics such as mean fibre diameter (MFD) and standard deviation (and coefficient of variation), spin fineness, curvature degree (and standard deviation), comfort factor, medullation percentage (by weight and number in white samples only) using traditional reference laboratory testing methods. Samples were scanned in a large cuvette using a FOSS NIRSystems 6500 monochromator instrument in reflectance mode in the Vis and NIR regions (400 to 2500 nm). Partial least squares (PLS) regression was used to develop a number of calibration models between the spectral and reference data. Mathematical pre-treatment of the spectra (second derivative) as well as various combinations of wavelength range were used in model development. The best calibration model was found when using the NIR region (1100 to 2500 nm) for the prediction of MFD, which had a coefficient of determination in cross-validation (R2) of 0.88 with a root mean square standard error of cross validation (RMSECV) of 2.62 μm. The results show the NIR technique to have promise as a semi-quantitative method for screening purposes. The lack of grease in alpaca wool samples suggests that the technique might find ready application as a rapid measurement technique for preliminary classing of shorn fleeces or, if used directly on the animal, the technology might offer an objective tool to assist in the selection of animals in breeding programmes or shows.