A wearable smart sensing system is capable of continuously monitoring biometric information such as respiration, pulse, and body temperature while attached to an arbitrary surface on the user's body to be utilized freely during activities. Research conducted on new materials, fabrication processes, structure of electrodes, and wireless communication technologies has made constant progress in the development of smart sensing systems that use entirely wearable forms of devices to go beyond conventional devices that are based on intrinsically rigid components, such as silicon. Among various platforms that can be used in the development of smart sensing systems, optoelectronics provides innovative sensing functions (e.g., human–machine interfaces and phototherapy) that can be transferred from traditional healthcare to smart healthcare, such as point of care. Optoelectronics are light-mediated displays that allow a light source to be controlled and a large light spectrum to be detected. Recently, this platform that uses smart and wearable optoelectronic sensing systems has become increasingly advanced to better help human beings treat their diseases through self-healthcare. Herein, recent advanced technologies in materials, structures, and wireless platforms for smart sensors using wearable optoelectronics are reviewed.