Previous research on sensory processing sensitivity and related concepts showed an association with internalizing problems. The current explorative study investigated the underlying factor structure of the parent-report Highly Sensitive Person Scale (HSPS) and its association with problems in daily functioning. Caregivers of 235 children (3–16 years) completed the HSPS as well as questions on daily functioning. First, the factor structure of the HSPS was explored and evaluated. Second, both differences in reported problems between a high SPS and a control group, and in SPS factors between children with few versus many problems, were examined. Results suggested that the scores of the HSPS have good internal consistency and supported a two-factor structure which distinguishes Overreaction to Stimuli (OS) and Depth of Processing (DP). Children with high SPS were reported to have more internalizing problems. High OS was more common in children who cried excessively as a baby, children with medically unexplained physical symptoms (MUPS), sleeping, eating and drinking problems while high DP was more common in children with MUPS and sleeping problems. This study provides the first empirical evidence that the parent-report HSPS may add valuable information to the assessment of children with problems in daily functioning.