HbA1c is the gold standard test for monitoring medium/long term glycemia conditions in diabetes care, which is a critical factor in reducing the risk of chronic diabetes complications. Current technologies for measuring HbA1c concentration are invasive and adequate assays are still limited to laboratory-based methods that are not widely available worldwide. The development of a non-invasive diagnostic tool for HbA1c concentration can lead to the decrease of the rate of undiagnosed cases and facilitate early detection in diabetes care. We present a preliminary validation diagnostic study of W-band spectroscopy for detection and monitoring of sustained hyperglycemia, using the HbA1c concentration as reference. A group of 20 patients with type 1 diabetes mellitus and 10 healthy subjects were non-invasively assessed at three different visits over a period of 7 months by a millimeter-wave spectrometer (transmission mode) operating across the full W-band. The relationship between the W-band spectral profile and the HbA1c concentration is studied using longitudinal and non-longitudinal functional data analysis methods. A potential blind discrimination between patients with or without diabetes is obtained, and more importantly, an excellent relation (R-squared = 0.97) between the non-invasive assessment and the HbA1c measure is achieved. Such results support that W-band spectroscopy has great potential for developing a non-invasive diagnostic tool for in-vivo HbA1c concentration monitoring in humans.