The circular continuum of values captures the conflicts and compatibilities among values. Although people can pursue the goals of competing (i.e., opposed) values, the theory postulates that they cannot do so in the same, single act. Surprisingly, this central assumption of the theory—the basis of the circular structure of values in real-time behavioral acts—has not been subject to a direct test. We fill this gap and differentiate two types of values: value-traits guide perception and behavior over time and situations and value-states guide real-time behavioral acts. We measured value-traits with the PVQ-RR and value-states with the experience sampling method (ESM) to tap motivations in real-time behavioral acts. The ESM permits assessment of value states experienced in natural settings, in real time, and across repeated occasions. A sample of 374 adult participants provided data on their value traits and reported real-time motivations for 13,873 behavioral acts. Relations among the value-states reproduce the circular structure of value traits. However, the hierarchy of value-states expressed in real-time behavior differs substantially from the hierarchy of value-traits measured by questionnaire. This may suggest that the importance of value-states depends more on situations than on the hierarchy of value traits.