Impulsivity is a key personality and psychopathology construct that is best conceptualized as multidimensional. The UPPS model is a comprehensive multidimensional framework which defines four impulsivity facets: negative urgency, lack of premeditation, lack of perseverance, and sensation seeking. Although these facets have unique predictive value in laboratory based correlational studies, the validity and expression of these facets have not been examined in daily life. The present study employed experience sampling methodology (ESM) to examine associations of UPPS impulsivity facets with affect, cognition, and behavior in daily life in a non-clinical sample of 299 young adults. The impulsivity facets were differentially expressed in daily life. Negative urgency was associated with negative affect, poor sense of self, and thought disruption; lack of premeditation was associated with negative but energetic affect; lack of perseverance was characterized by difficulty putting forth effort and completing activities; and sensation seeking was associated with positive affect and enjoying oneself. All UPPS facets with the exception of sensation seeking were associated with increased troublesome behavior in daily life. Overall, these results support the validity of the multidimensional UPPS model of impulsivity in daily life and suggest that ESM is a useful tool for examining the expression of impulsivity.