Autism spectrum disorder (ASD) is a pervasive developmental disease characterized by persistent impairment, repetitive and stereotypical behaviors in social interaction, as well as restricted interests and activities. The etiology of ASD is not clear yet, which results in difficulties in clinical diagnosis and treatment, and also brings heavy burden to patients and society. Positron emission tomography (PET) is a frequently used molecular imaging technology in quantitative, dynamic and in vivo research for therapeutic efficacy evaluation, pathophysiological mechanism investigation, thereby promoting development of ASD therapeutic drugs. More and more imaging studies have been reported on ASD recently, and the physiological changes featured by PET have been disclosed. This chapter reviews the specific radioligands for PET imaging of critical biomarkers involved in ASD. Herein, we discuss cerebral blood perfusion, cerebral glucose metabolism, and neurotransmitter system (transporters, precursors and receptors), as well as some other novel targets, including arginine vasopressin receptor targets and neuroinflammation related targets. The status of application and future prospect of the PET technology in research of ASD were discussed. This chapter provides a detailed and comprehensive literature review on ASD PET probe development, thereby can help readers intuitively and conveniently understand the status quo of research on ASD PET, and develop new research directions in this field.