This is part of the US-based firm's focus on bringing Internet to everyone in India, which has the world's second largest population.
"100 stations will have wi-fi by December 2016. Mumbai Central (station) to go live by January. This is in partnership with RailTel," Pichai said at a Google for India event.
The telecom wing of the Indian Railway, RailTel, had signed an agreement with the subsidiary of Google India to provide wi-fi facilities at 400 stations across the country.
During his two-day visit, Pichai will meet President Pranab Mukherjee and Prime Minister Narendra Modi. He will also address students at a Delhi University college.
"Our focus on bringing Internet access to everyone, making sure our products are working for them in a meaningful way and then ensure our platform allows them to add their voice to the Internet," the India-born CEO said.
Pichai, who is on his maiden visit to India after taking over as the CEO of Google earlier this year, said the company is also expanding its headcount in India, especially in engineering operations.
"Google is looking at hiring people for Bangalore and Hyderabad... We will also build huge new campus in Hyderabad to build capabilities," he said.
Pichai said as part of Google's efforts to help women get online, the company is expanding bicycle for women programme nationally.
"From a pilot, we will now expand the programme to cover three lakh villages in three years," he said.