Sun‐induced fluorescence (SIF) has been found to be strongly correlated with gross primary production (GPP) in a quasi‐linear pattern at the scales beyond leaves. However, the causes of the GPP:SIF relationship deviating from a linear pattern remain unclear. In the current study conducted at two maize sites in Nebraska in 2017 summer growing season, we investigated the relationship between GPP and SIF at 760 nm (F760) at two temporal scales and quantified the contributions of incoming photosynthetically active radiation (PARin), fraction of absorbed PAR (fPAR), light use efficiency (LUE), and F760 yield (F760,y, defined as F760/(PARin×fPAR)) to GPP and F760 variabilities to further understand the linearity and deviations in the GPP:F760 relationship. We found the following: (1) For individual growth stages when canopy structure and chlorophyll content were stable, GPP and F760 were strongly controlled by PARin, while LUE and F760,y had much lower contributions to the GPP:F760 relationship; during this period, LUE and F760,y had either a slightly negative or no clear relationship, which explained some deviations in the GPP:SIF relationship. (2) At the seasonal scale, the contribution of LUE to GPP variability as well as the contribution of F760,y to F760 variability increased and was comparable to the contribution of PARin; the LUE:F760,y relationship showed a strong linear relationship, which strengthened the linear GPP:F760 relationship. Both maize sites showed similar patterns. A framework was applied to estimate LUE at individual stages and as a result, significantly improved the GPP estimation, thus enhancing the SIF potential for inferring photosynthesis.