A highly efficient cascade bicyclization reaction of o-alkenylphenyl isothiocyanates with propargylamines has been developed, which affords a series of thiazolo[2,3-b]quinazolines in good to excellent yields by using K2CO3 as a base in MeCN at 80 °C. This method is transition-metal-free and operationally simple with broad functional group tolerance. Mechanistically, 6-exo-trig hydroamination followed by 5-exo-dig hydrothiolation was involved in this transformation.