Attention-deficit/hyperactivity disorder (ADHD) is one of the most frequently diagnosed disorders in childhood affecting around 3% to 5% of adults worldwide. Most of the studies have been carried out using the Five Factor Model (FFM). Given the value and importance of describing adult ADHD in terms of general personality structure for a better conceptualization of this disorder, this study contributes adding new data on an Alternative Five Factor Model (AFFM) of personality. The aim of the present study is twofold: To assess the personality profile of adults with ADHD under the AFFM perspective, and to test the discriminant validity of the Zuckerman-Kuhlman Personality Questionnaire (ZKPQ) in differentiating ADHD subjects vs. normal range controls. A sample of 217 adults (64% male) meeting ADHD diagnosis (DSM-IV) was paired by age and sex with 434 normal-range controls. Logistic regression analysis showed that high scores on Neuroticism-Anxiety, Impulsivity and General Activity, and low on Work Activity were the most powerful predictors of being endorsed with an ADHD diagnosis. Results may suggest refinements in the personality assessment of ADHD as it seems that the ZKPQ provides more specific subscales for the description and conceptualization of this disorder.