Venezuela had seven different capitals, caracas being one at least by 5 times, the easiest candidate would be maracay as it had been roughly 30 years under Gomez' government, just avoid the capital being moved back to Caracas after his death in 1936...
Well, if we are talking about Venezuela´s Alternate Capitals there is an interesting list of possible cities, however I am not sure if the country really had 7 different ones (Unless you are counting the capitals of the Province of Venezuela, that existed before the Spanish created the Captaincy General of Venezuela by joining the provinces of Maracaibo, Margarita, Cumaná, Guayana, Trinidad, and Venezuela under the same administrative division.)
If we use the full options of the scenario (that includes the foundation of new cities) I believe that this could be a good list of alternate capitals of Venezuela:
*Valencia (It was declared capital of the Confederation of the United Provinces of Venezuela by the National Congress on January 9, 1812 and it was the provisional capital of the Republic in the years 1830 and 1858.)
*Maracay (As JDF_01 said, it worked as a Capital of Venezuela under the Dictatorship of Juan Vicente Gómez. However, it was a Capital
de facto, no
de iure. Caracas remained the
de iure Capital of the Republic, but in the era of the
Gomecismo, the real capital was wherever Gómez would be, and he preferred Maracay.)
*Coro (First capital of the Province of Venezuela. It was the administrative capital from 1527 to 1546. It remained the ecclesiastical capital until 1637.)
*El Tocuyo (Replaced Coro as the Capital of the Province until 1577, when it was replaced by Caracas.)
*Cumaná (The oldest continuously-inhabited, European-established settlement in South America, it was the capital of its own province and department but like Coro or El Tocuyo, it never was the Capital of the whole country.)
*Maracaibo (In the
Carta de Jamaica, Simón Bolivar,
the Liberator, when he speculated about the fate of New Granada and Venezuela, imagined that the two would unite in a single country, that if it were to become a central republic it would have as capital Maracaibo or a city with the name of Bartolomé de las Casas. Bolivar wrote: "
La Nueva Granada se unirá con Venezuela, si llegan a convenirse en formar una república central, cuya capital sea Maracaibo, o una nueva ciudad que, con el nombre de Las Casas (en honor de este héroe de la filantropía), se funde entre los confines de ambos países, en el soberbio puerto de Bahía Honda." Translation
: The New Granada will unite with Venezuela, if they agree to form a central republic, whose capital is Maracaibo, or a new city that, under the name of Las Casas (in honor of this hero of philanthropy), merges between the confines of both countries, in the superb port of Bahia Honda. As Cumaná, Maracaibo was the Capital of its own province and department
. In fact, unlike Cumaná, Maracaibo was the Capital of a Captaincy General, when the Cádiz Cortes erected the Province of Maracaibo as one, separated from Venezuela, decision revoked by Ferdinand VII once he returned to the throne. However, Maracaibo never was the Capital of the whole country or of an entity called Venezuela.)
*Las Casas City in Bahia Honda (As said above, Bolívar imagined a city built in Bahia Honda under the name of Las Casas to work as the Capital of an Union between Venezuela and New Granada. However, currently Bahia Honda is part of the territory of modern Colombia, not of Venezuela.)
From this list, the last two can work as alternate capitals of Gran Colombia, or even in the case of Bahia Honda, as a capital of modern Colombia (New Granada).
*Note: When I am talking about departments, I am talking about the departments of the Republic of Colombia know today as Gran Colombia.