In May 1791, the Caracas Council (Cabildo) gave him a position as teacher in the "Reading and Writing School for Children". In 1794, he presented his critical writing "Reflection on the flaws vitiating the Reading and Writing School for Children in Caracas and Means of Achieving its Reform and a New Establishment" to the council. It's an original approach to a modern school system.
His role in the failed Gual and Espańa conspiracy against the spanish crown in 1797 forced him to leave Venezuela.
In Kingston, Jamaica he changed his name to Samuel Robinson, and after staying some years in the United States he traveled to France (1801). There, in 1804, he met his former tutee, and together they made a long journey across Europe. They witnessed the coronation of Napoleon Bonaparte in Milan, as King of Italy and in Rome, he witnessed how Bolívar took his famous oath that he would liberate all of America from the Spanish Crown, and registered it for history.
Between 1806 and 1823 he lived alternatevily in Italy, Germany, Prussia, Poland and Russia. He would say, about his life in Europe: "I stayed in Europe for more than twenty years; I worked in an Industrial Chemistry Laboratory [...] attended some secret socialist-oriented meetings [...] studied a little literature; learned languages and directed a Reading and Writing School in a small russian town".
He returned to America in 1823, using his name "Simón Rodríguez" again. In Colombia he established a first workshop-school in 1824. He was called to Peru by Simón Bolivar and became "Director for Public Education, Physical and Mathematical Sciences and Arts" and "Director of Mines, Agriculture and Public Roads" of the Bolivian Republic.
In 1826 he established a second workshop-school, as part of a project for all Bolivia. But Antonio José de Sucre, president of Bolivia since October 1826, didn't have a good relationship with him, and Rodríguez resigned the same year, working during the rest of his life as educator and writer, living alternatively in different places of Peru, Chile and Ecuador. Very important is his work "Sociedades Americanas" ("American Society"), which was divided in several issues published in Arequipa in 1828, in Concepción in 1834, Valparaiso in 1838 and Lima, in 1842.