A large lateral photovoltaic effect (LPE) with a fast optical response time is necessary to develop high-performance position-sensitive detectors. In this paper, we report an LPE with a high self-powered position sensitivity and ultrafast optical relaxation time in S n S 2/n-S i junctions prepared using pulsed laser deposition. A large built-in electric field was generated at the S n S 2/S i interface, which resulted in a large LPE with a positional sensitivity of up to 116 mV/mm. Furthermore, the measurement circuit with multiple parallel resistors had a strong influence on the ultrafast optical response time of the LPE and the fastest optical relaxation time observed was ∼0.44µs. Our results suggest that the S n S 2/S i junction would be a promising candidate for a wide range of optoelectronic device applications.