Background: Most adolescent smokers start smoking before the age of twelve. Little is known about the behavioural smoking determinants of Dutch primary school children. Methods: A cross‐sectional study was carried out on a sample of students from the final year of 143 Dutch primary schools. A total of 3700 students (mean age =11.6 years) completed a questionnaire based on the ASE model, measuring the attitude, social influences and self‐efficacy expectations concerning smoking. Results: Students were categorized as never smokers (64.3%), experimental smokers (28.0%), and regular smokers (7.8%). Multinomial logistic regression analyses showed that never smokers were younger, and were more often female, religious and from two‐parent families than experimental smokers. Never smokers perceived more disadvantages, long‐term physical consequences, more negative social norms and less pressure regarding smoking, higher self‐efficacy expectations towards non‐smoking, and had fewer parents, siblings or best friends who smoked. Looking at differences between experimental and regular smokers showed that experimental smokers received less pocket money. They also perceived more disadvantages, fewer advantages, more negative social norms and less pressure towards smoking, higher self‐efficacy expectations towards non‐smoking, and were less likely to be surrounded by friends, peers, family or teachers who smoked. Generally, the low scores for physical consequences and risk perception regarding addiction were striking. Conclusions: Smoking prevention aimed at primary schoolchildren should consider the different smoking categories, with their specific motives and influences. For instance, the influences on smoking initiation of parents, siblings and best friends suggest more comprehensive programmes aimed at the entire family. Youngsters' ignorance of addiction needs more attention.