Young children’s mastery motivation and neurodevelopmental evaluation can contribute to overall early assessment for early intervention evaluation. At present, children born preterm (<37 weeks gestation) and with a low birth weight (LBW; <2500 g) are at increased risk of experiencing developmental delays and more nuanced cognitive and language challenges. The main objective of this exploratory study was to examine the connection between preterm children’s mastery motivation and their neurodevelopment, as well as to determine whether assessing mastery motivation can enhance assessment practices for early intervention (EI) programs. Parents of children born preterm completed the revised Dimensions of Mastery Motivation Questionnaire (DMQ18). Neurodevelopment was measured on the Bayley Scales of Infant and Toddler Development (BSID-III). Results revealed significant correlations between DMQ18 and BSID-III measures. Multivariate analysis showed that infants and toddlers born with a very low birth weight (VLBW; <1500 g) scored significantly lower on the infant DMQ18 and the BSID-III measures. Regression analyses revealed that birth weight and home environment were significant predictors of the children’s eligibility for EI programs. Infants’ social persistence with other children, gross motor persistence, and mastery pleasure, as well as toddlers’ objective cognitive persistence, social persistence with adults, gross motor persistence, mastery pleasure, and negative reaction to frustration, were important markers for evidenced-based practices in EI programs. This study demonstrates the utility of the DMQ18 as a contributory assessment measure and the importance of birth weight and home environment in predicting EI enrollment.