Photoactive composites comprising polyaniline and metallurgical silicon powder were prepared by an in situ two‐step procedure (pSi‐PANI). Their structures were elucidated by electronic and infrared spectroscopy and powder X‐ray diffraction (P‐XRD) techniques. The P‐XRD revealed that the acid‐doped green composites (pSi‐PANI·HCl and pSi‐PANI·HF) acquire a two‐dimensional crystalline array structure featuring nanosheet morphology. The photoconductivity and photovoltaic (PV) properties of these composites were examined as flexible microscopic films of finely dispersed composites in a dry linseed oil matrix sandwiched between two aluminium electrodes, [Alperforated/pSi‐PANI/Alplate]. The hybrid composites display a thermal voltage in the dark but develop a photocurrent under weak illumination (incandescent lamp, 75.4 µW cm–2). These green composites exhibit enhanced power conversion efficiency (Jsc = 16.7–34.0 μA cm–2, Voc = 0.86–1.21 V, η = 5.2%–11.4%) compared with their undoped blue analogs (Jsc = 1.3–6.1 μA cm–2, Voc = 0.18–1.02 V, η = 0.1%–2.1%). The pSi‐PANI·HCl composite is a promising candidate for the development of a low‐cost, easily processed, flexible PV system that can be scaled up for large‐area indoor applications. © 2012 Society of Chemical Industry