Under operation "Safe Homeland", 3,000 soldiers will patrol the streets of the capital Caracas and other cities.
President Maduro said the plan would bring peace to Venezuela, which has one of the highest homicide rates in South America.
The opposition has long criticised the government's record on crime, and used it as a campaign issue in recent polls.
The government says more than 16,000 people were killed in crimes in 2012, a rate of 54 per 100,000.
However the Venezuela Violence Observatory, a campaign group, put last year's murder rate much higher - at 73 per 100,000 people.
Opposition leader Henrique Capriles, who is contesting Mr Maduro's narrow victory in last month's presidential election, highlighted crime rates during the campaign.
Under the operation Safe Homeland soldiers will patrol the country's 79 most crime ridden areas - including four in Caracas.
Speaking on Monday, Mr Maduro said his government was "revising every aspect to build a peaceful country."
Last year, the government introduced a new gun law banning the sale of firearms and ammunition.
Crime figures have been rising steadily since the late president Hugo Chavez took office in 1999.
Venezuelan President Nicolas Maduro has launched a massive security plan aimed at curbing street crime.