Groundwater contributions to streamflow sustain aquatic ecosystem resilience; streams without significant groundwater inputs often have well-coupled air and water temperatures that degrade cold-water habitat during warm low flow periods. Widespread uncertainty in stream-groundwater connectivity across space and time has created disparate predictions of energy and nutrient fluxes across headwater networks, hindering predictions of cold-water habitat resilience under climate change scenarios. Recently, annual paired air and water temperature signals have been harnessed to indicate stream water thermal sensitivity and the dominance of deep versus shallow groundwater influence, although the utility of diel air–water temperature signal metrics for hydrologic inference has remained unexplored. Here we analyzed two consecutive years of locally paired, air–water temperature data from 47 headwater stream sites in the Catskill Mountains, New York, USA, and discovered characteristic seasonal patterns in diel temperature signal sinusoid metrics (amplitude ratio, phase lag, and mean ratio) driven by shifts in streamflow generation mechanisms and stream network position. Hydrologic interpretations of observed patterns were supported by stream heat budget model scenarios and additional analysis of paired air–water temperature data from two streams in Shenandoah National Park, Virginia, USA, with well characterized stream-groundwater connectivity. We found that within smaller tributaries, streamflow generation transitions from runoff to groundwater dominance were driven by hillslope drying during seasonal periods of lower precipitation. This was evidenced by significant correlations (p < 0.01) between daily water:air temperature signal amplitudes (non-linear decreases of ∼ 50 %) and derived base-flow index at 22 of the 28 sites, indicating enhanced local groundwater influence on streamflow promotes decoupling of diel air–water temperature signals. Additionally, ratios between daily water:air temperature signal means were lower in tributaries (∼0.68) when compared to main-stem (∼0.8) sites, increasing linearly throughout the observational period. In conceptual stream heat budget models, groundwater inflow had minimal effects on daily phase lags (∼0.2 hr), but increases in fractional groundwater discharge (0–50 %) depressed daily amplitude (∼20 % to 50 %) and mean ratios (∼15 %), supporting the sensitivity of daily metrics to interpreted changes in seasonal groundwater contributions to streamflow. During observational periods (i.e., April through October 2021 and 2022), significant differences (p < 0.01) between tributary and main-stem air–water metrics occurred when base-flow contributions were highest (∼0.93 vs. ∼ 0.68), as sites lower in the network had daily temperature metrics dominated by stream channel thermal inertia, rather than local groundwater connectivity, showing enhanced air–water diel signal coupling during warmer, drier periods. Divergent air temperature coupling across the network was interpreted as being driven by distance from local groundwater source zones, additional lateral groundwater inflows do not contribute a meaningful fraction to channel discharge lower in the network. Given the growing footprint of stream temperature observations, diel air–water temperature signals can provide distributed metrics sensitive to upstream groundwater discharge. Consequently, these metrics can support ongoing efforts by resource managers and researchers seeking to forecast the resilience of cold-water habitat to climate warming and changing precipitation regimes in mountain headwater streams.