Wearable sensors are promising instruments for conducting both laboratory and ambulatory research in psychophysiology. However, scholars should be aware of their measurement error and the conditions in which accuracy is achieved. This study aimed to assess the accuracy of a wearable sensor designed for research purposes, the E4 wristband (Empatica, Milan, Italy), in measuring heart rate (HR), heart rate variability (HRV), and skin conductance (SC) over five laboratory conditions widely used in stress reactivity research (seated rest, paced breathing, orthostatic, Stroop, speech task) and two ecological conditions (slow walking, keyboard typing). Forty healthy participants concurrently wore the wristband and two gold standard measurement systems (i.e., electrocardiography and finger SC sensor). The wristband accuracy was determined by evaluating the signal quality and the correlations with and the Bland-Altman plots against gold standard-derived measurements. Moreover, exploratory analyses were performed to assess predictors of measurement error. Mean HR measures showed the best accuracy over all conditions. HRV measures showed satisfactory accuracy in seated rest, paced breathing, and recovery conditions but not in dynamic conditions, including speaking. Accuracy was diminished by wrist movements, cognitive and emotional stress, nonstationarity, and larger wrist circumferences. Wrist SC measures showed neither correlation nor visual resemblance with finger SC signal, suggesting that the two sites may reflect different phenomena. Future studies are needed to assess the responsivity of wrist SC to emotional and cognitive stress. Limitations and implications for laboratory and ambulatory research are discussed.