The invention discloses an asymmetric photoelectric active thiacalixarene [4] acceptor molecule and a compounding method thereof. The method is characterized by successfully compounding the asymmetric photoelectric active thiacalixarene [4] acceptor molecule containing ferrocene and rhodamine b groups by successively introducing an electrochemical probe and a fluorescence probe into a thiacalixarene [4] structure platform by utilizing asymmetric design and then performing stepping selective acylation reaction of thiacalixarene [4]-1,3-diamine. The technique according to the invention supplies a new method for designing and compounding the asymmetric photoelectric active thiacalixarene [4] acceptor molecule with photoresponse center and electroresponse center, establishes a basis for realizing the photoelectric two-channel response detection for the acceptor molecule and has significance in expanding the application thereof in super-molecular recognition.