It met from February 15, 1819, established the new independent-from-Spain nation on December 17, was interrupted by further independentist activity, and reconvened on July 31, 1821, when the Congress of Cúcuta began its sessions.
Important parts of the countries were still under Spanish rule, so elections only took place in the areas of southern Venezuela and Margarita Island controlled by the patriot forces.
At its first meeting on February 19, 1819, Bolivar gave his famous Address at Angostura, but not all of the proposals contained in it were accepted (most notably the suggestions of a highly exalted ceremonial president-for-life who would govern through powerful ministers accountable to parliament and a hereditary senate, both modeled on the British example, and a "fourth" branch of government, the "moral" one, loosely modeled on the Classical Areopagus).
Its culminating piece of legislation was the Venezuelan Constitution of 1819, officially adopted on August 15, but quickly made obsolete by the creation of the Republic of Colombia on December 17, 1819.
Basically, the document explained how Colombia was going to be as an independent nation, in relation to the reasons that motivated the political union of Venezuela and New Granada.