Technically, that should be trois virgule quatorze (as this answer states too) but in that particular case, most people I know just say trois-quatorze.
Pourquoi la quadrature du cercle est-elle impossible ? Trois-quatorze-quinze... cette ritournelle bien connue décrit le rapport, appelé nombre Pi, entre la circonférence d'un cercle et son diamètre.
Joaquín Navarro, Les secrets du nombre π, 2011.
I have never heard anyone saying trois virgule un quatre. That would be considered kind of "illiterate", done by someone unable to build numbers from digits. Only the digit 0, especially a leading one, is pronounced individually.
We also generally omit to name the decimal separator or the unit when talking about temperatures or sometimes with prices, e.g. Trente-sept deux le matin (37°2 le matin).
An alternate way, taught at school but rarely used otherwise, is to use a unit for the decimal part:
3,14 : trois quatorze centièmes
3,14159 : trois quatorze mille cent cinquante-neuf cent-millièmes.
See also Comment prononcer les nombres à virgule ?
In France, like in Germany I believe, decimal numbers are expected to be written with a comma, not a decimal point: 3,14.