The photochemical reflectance index (PRI) is regarded as a promising proxy to track the dynamics of photosynthetic light use efficiency (LUE) via remote sensing. The implementation of this approach requires the relationship between PRI and LUE to scale not only in space but also in time. The short-term relationship between PRI and LUE is well known and is based on the regulative process of non-photochemical quenching (NPQ), but at the seasonal timescale the mechanisms behind the relationship remain unclear. We examined to what extent sustained forms of NPQ, photoinhibition of reaction centres, seasonal changes in leaf pigment concentrations, or adjustments in the capacity of alternative energy sinks affect the seasonal relationship between PRI and LUE during the year in needles of boreal Scots pine. PRI and NPQ were highly correlated during most of the year but decoupled in early spring when the foliage was deeply downregulated. This phenomenon was attributed to differences in the physiological mechanisms controlling the seasonal dynamics of PRI and NPQ. Seasonal adjustments in the pool size of the xanthophyll cycle pigments, on a chlorophyll basis, controlled the dynamics of PRI, whereas the xanthophyll de-epoxidation status and other xanthophyll-independent mechanisms controlled the dynamics of NPQ at the seasonal timescale. We conclude that the PRI leads to an underestimation of NPQ, and consequently overestimation of LUE, under conditions of severe stress in overwintering Scots pine, and most likely also in species experiencing severe drought. This severe stress-induced decoupling may challenge the implementation of the PRI approach.