With five trillion generated per year, cigarette butts are some of the most common litter worldwide. However, despite the potential environmental and human health risks from cigarette butts, little effort has been made to understand airborne emissions from cigarette butts. This study examined the influence of temperature, relative humidity and water saturation on airborne chemical emissions from cigarette butts. Experiments were conducted to measure the emitted chemical masses from butts using headspace analysis after the butts were conditioned in a controlled chamber under four conditions (30 °C and 25% relative humidity (RH), 30 °C and 50% RH, 40 °C and 25% RH, 40 °C and 50% RH) and in an outdoor environment (two sets of experiments in both summer and winter). The measured target chemicals included furfural, styrene, ethylbenzene, 2-methyl-2-cyclopenten-1-one, limonene, naphthalene, triacetin, and nicotine. Results indicate that increased temperature increased the emission rates of all target chemicals from the butts conditioned in both chambers and outdoors. In addition, water has considerable influence on the emission rates from the butts. Seven of the eight chemicals were emitted faster from butts at 50% RH compared to 25% RH. During water saturation, chemicals with high water solubility and partition coefficient between water and air, e.g., triacetin and nicotine, mainly migrate into the surrounding environment via aqueous rather than airborne routes. This highlights the importance of rainfall events on airborne emission variability for triacetin and nicotine. Water saturation increased the decay rate (decreased the decay time) of emitted mass measured in headspace analysis for the two carbonyl chemicals: furfural and 2-methyl-2-cyclopenten-1-one, while it decreased the decay rate (increased the decay time) for the three hydrocarbons (styrene, limonene, and naphthalene).