A kind of functional noble metal nanoparticles and metal/organic semiconductor composite nanomaterials, Ag nanoparticles (AgNPs, 6–10 nm in diameter) decorated small-sized Ag-tetracyano-p-tetrafluoroquinodimethane (AgTCNQF4) nanorods (150–400 nm in length and 60–100 nm in diameter), have been successfully synthesized through a rapid microemulsion reaction between TCNQF4 molecules and an AgNP colloid under a soft template of poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol). The morphology, chemical structure, and elemental composition of the prepared AgNPs–AgTCNQF4 composite nanorods were studied by transmission electron microscopy, selected-area electron diffraction, and X-ray photoelectron spectroscopy. The real-time ultraviolet–visible spectroscopy assisted with two-dimensional correlation spectroscopic analysis was employed to explore the growth of AgNPs–AgTCNQF4 composite nanorods in microemulsion. These composite nanorods display the photoinduced charge transfer (CT) property from the monoanion (TCNQF4 –) to dianion (TCNQF4 2–) selectively under 532 nm light irradiation. The larger content of AgNPs on the surface of AgTCNQF4 led to the higher conversion of dianion due to the plasmon-assisted photocatalysis. This photoelectric composite material is promising for the applications of light-writing data storage and photocatalysis.