Nano-roughened Teflon-like film coated poly-crystalline Si photovoltaic solar cells (PVSCs) with enhanced surface hydrophobicity and conversion efficiency (η) are characterized and compared with those coated by a Si nanorod array or a standard SiN anti-reflection layer. The Teflon-like film coated PVSC surface reveals a water contact angle increasing from 89.3° to 96.2° as its thickness enlarges from 22 to 640 nm, which is much larger than those of the standard and Si nanorod array coated PVSC surfaces (with angles of 55.6° and 32.8°, respectively). After nano-roughened Teflon-like film passivation, the PVSC shows a comparable η(10.89%) with the standard SiN coated PVSC (η = 11.39%), while the short-circuit current (I(SC)) is slightly reduced by 2% owing to the slightly decreased UV transmittance and unchanged diode performance. In contrast, the Si nanorod array may offer an improved surface anti-reflection with surface reflectance decreasing from 30% to 5% at a cost of optical scattering and randomized deflection, which simultaneously decrease the optical transmittance from 15% to 3% in the visible region without improving hydrophobicity and conversion efficiency. The Si nanorod array covered PVSC with numerous surface dangling bonds induced by 1 min wet-etching, which greatly reduces the open-circuit voltage (V(OC)) by 10-15% and I(SC) by 30% due to the reduced shunt resistance from 3 to 0.24 kΩ. The nano-scale roughened Teflon-like film coated on PVSC has provided better hydrophobicity and conversion efficiency than the Si nanorod array covered PVSC, which exhibits superior water repellant performance and comparable conversion efficiency to be one alternative approach for self-cleaning PVSC applications.