A needle-solid-phase microextraction (SPME) method based on hybrid monolithic column (HMC) was proposed for simultaneous separation and extraction of seven amphetamine-type stimulants (ATSs) (amphetamine, methamphetamine, cathinone, methcathinone, 3,4-methylenedioxyamphetamine, 3,4-methylenedioxymethamphetamine, and 3,4-methylenedioxyethylamphetamine), combining with ultra-performance liquid chromatography-triple quadrupole/linear ion trap mass spectrometer (UPLC-QTRAP MS/MS). Thiol functionalized HMC (T-HMC) showed high extraction efficiency and excellent elution results towards target analytes, among three kinds of single/bi-functionalized HMCs. Various parameters of SPME operation and analytical performance were investigated systematically. The adsorption mechanism of T-HMC to ATSs was also discussed and explained as a mixed mode of electrostatic and hydrophobic interactions. Under the optimum experimental conditions, the proposed T-HMC needle-SPME-UPLC-QTRAP MS/MS method was rapid and convenient with good accuracy, low sample consumption, high sensitivity and strong anti-interference ability. This method was successfully applied to quantitative determination of seven trace ATSs in complex sewage and urine samples. In view of abundant types of HMCs, the needle-SPME based on functional HMC also had the potential to selectively separating and enriching other tract new psychoactive substances in complex matrices, and could provide a reliable tool for drug monitoring, especially in applications for forensic analysis and drug abuse.