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Both of the words are kind off synonyms or meaning of each other

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    Take a look at the sections titled "Speaking About The Meaning of loquacious" and "Synonym Discussion of loquacious" in the Merriam-Webster.com entry for the word loquacious. LDOCE says, further, that loquacious belongs to the formal register of English.
    – user3395
    Mar 30, 2018 at 9:58
  • In my experience, talkative people talk a lot but loquacious people talk even more.
    – Ronald Sole
    Mar 30, 2018 at 10:10
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    To state the matter very briefly, the English language is a hybrid of German and Latin (Latin via French mainly, but sometimes directly). English started out as a dialect of German but then in the 11th century, with The Norman Conquest, French became a very strong influence on English. English often has two words for the same thing, an English word and a word derived from Latin (usually via French). Uneducated and under-educated speakers are not likely to know the Latin-derived word because these words appear mainly in books and these words are used mainly by speakers who read a lot of books.
    – TimR
    Mar 30, 2018 at 12:05

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The difference is one of register

Loquacious is from a very high register. Talkative is a normal mid-register word.

Looking around the web, most of the actual use of "loquacious" is ironic.

The worst thing for a writer is to be loquacious with verbocity.

I have also seen other advice that one should avoid words like "loquacious", as you will seem to be trying to sound smart (by using rare words) but you will actually sound pretentious.

Learners should normally use "talkative".

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    Your language survey ignores texts not published on the internet and will be biased toward the snippy speech of millennials that believe they invented irony.
    – m_a_s
    Mar 30, 2018 at 13:42
  • Well, ironically the quote I gave is a paraphrase of St Augustine, from the Confessions, (orginally in Latin, c. 400AD.)
    – James K
    Mar 30, 2018 at 13:52
  • Perhaps a bit ironic. :-) However, I did say there was bias, not that the internet lacked texts from before 1987.
    – m_a_s
    Mar 30, 2018 at 14:07
  • Yes, and English is filled with this fact.
    – Lambie
    Mar 30, 2018 at 14:11
  • @JamesK By the way, Anglo Saxon grammar has changed a bit since 400AD---not that St. Augustine spoke much. What St. Augustine actually said was "et vae tacentibus de te, quoniam loquaces muti sunt." He was not decryiing the word "loquacious" but making the point that some people talk much but say nothing---especially the ones who disagree with him. (St. Augustine text from his Confessions: faculty.georgetown.edu/jod/latinconf/1.html)
    – m_a_s
    Mar 31, 2018 at 2:50
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There are two subtle differences between talkative and loquacious.

Talkative

You can be called talkative without necessarily being attributed a characteristic of your personality. In other words, take the following example, "Sally always gets so talkative after she drinks coca-cola."

Sally is not always talkative, but only after she drinks coca-cola. It can be a temporary condition, in other words. Talkative also has a slightly negative connotation.

Loquacious

If you are called loquacious, then it is a personality trait and not something that is likely going away anytime soon. To the contrary of "talkative", loquacious can have a positive connotation. Though more often than not, it is used in a sardonic sense, like you're trying to use a euphemism.

"Lets say, Sally is loquacious.. she tends to ramble especially when she's nervous."

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