A novel nanocomposite of P3HT and Ag nanoparticles (Ag-P3HT) has been synthesized by laser ablation. The fluorescence wavelength of the nanocomposite can be tuned by varying the ablation duration. The steady-state emission maximum at 580 nm for pristine P3HT shows significant blueshift to wavelengths ranging from 520 to 550 nm for Ag-P3HT. NMR, FTIR and XPS spectroscopy confirm that chemical links are formed between P3HT and silver nanoparticles (NPs) in the nanocomposite. For the sample with an emission maximum at 530 nm, 1H NMR spectra indicate that 66% of the P3HT thiophene ring protons are replaced by Ag NPs. Time-resolved spectroscopy demonstrates that charge transfer efficiency increases for Ag-P3HT and this is attributed to the enhanced intimate interfacial contact between the chemically-bonded metal NPs and polymer chains. The synthetic route outlined provides a one-pot and green strategy for producing metal-organic polymeric materials, with controlled luminescence wavelengths and efficient photoinduced charge transfer that meet the requirement for developing high-performance organic light-emitting and photovoltaic devices.