Guerrero, top scorer at the Copa America in which Peru finished third, scored in the 47th and 73rd minutes as he combined with fellow striker Claudio Pizarro, back in the side after missing the tournament in Argentina through injury.
With Ecuador winger Antonio Valencia inspirational, strikers Jaime Ayovi and Cristian Benitez scored in the opening half hour at the Atahualpa, nearly 3,000 metres above sea level, against a Venezuela side lacking several first choice players kept fresh for the home clash with Argentina on Tuesday.
In Tuesday's other matches, Colombia travel to play Bolivia at high altitude in La Paz, Uruguay visit Paraguay in Asuncion for a repeat of July's Copa America final and Chile host Peru.
Peru's Paolo Guerrero (right) celebrates with team-mate Juan Vargas after scoring against Paraguay during their 2014 World Cup qualifying football match
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