Inhalant misuse is a worldwide problem, especially among adolescents. Toluene is the most widely misused inhalant. One hallmark of adolescence is the emergence of sexual behaviour, which can be affected by drug use. The aim of this study was to analyse the effects of toluene inhalation on different aspects of male rats’ sexual behaviour using a binge pattern of exposure in adolescent rats. Male Wistar rats were individually exposed to air or 6,000 ppm toluene for 30 min (acute exposure; n = 8 each) or twice a day for 12 days (repeated exposure; n = 9 each) in static exposure chambers. Independent groups of sexually experienced, adolescent rats (postnatal day 63, PN63) were tested after acute toluene exposure for copulation, sexual incentive motivation or noncontact erections. Sexually naïve, adolescent rats (PN45–59) were repeatedly exposed to toluene and tested for sexual behaviour after completing the 1st, 3rd, 5th, 7th, 9th, 11th and 13th exposure sessions. Acute toluene exposure impaired copulatory performance, diminished sexual incentive motivation and delayed noncontact erection occurrence in sexually experienced rats. Repeated toluene exposure during adolescence completely inhibited the onset of copulatory behaviours in sexually naïve rats, at the time at which they should have appeared. However, once the inhalant exposure ended, copulatory responses appeared gradually, and animals attained a typical, stable copulatory pattern. In conclusion, acute toluene exposure impairs sexual behaviour in young, sexually experienced animals, while repeated toluene exposure during adolescence prevents the onset of copulatory behaviour, although this effect is transitory. We analysed the effects of single and repeated toluene inhalation (6,000 ppm) on sexual behaviour of adolescent male rats. Acute toluene exposure impaired copulatory performance, diminished sexual incentive motivation and delayed noncontact erection in sexually experienced rats. Repeated toluene exposure during adolescence inhibited the onset of copulatory behaviours in sexually naïve rats. Data highlight the behavioural disruption produced by drug misuse during a critical developmental period.