As some of the comments have already pointed out, the basic book document class does not offer a macro called \subtitle.
A general observation: When working with the book document class, the basic LaTeX \title, \author, and \date commands may not be sufficiently rich/flexible for you, i.e., they may not let you generate an elaborate title page. If that's the case for your document, do look into using various LaTeX packages that provide lots of extra flexibility.
If you don't want to go that route and simply wish to insert the subtitle string in a font that's slightly smaller than that of the main title string, you may do so by employing the code, shown below, that generates the following screenshot.

\documentclass[french]{book}
\usepackage{babel}
\usepackage{iftex}
\ifpdftex
\usepackage[T1]{fontenc}
\usepackage{cfr-lm} % or: "\usepackage{lmodern}"
\else
\usepackage{fontspec}
\setmainfont{Latin Modern Roman}[Numbers=OldStyle]
\fi
\begin{document}
\frontmatter
% Default relative font size for argument of \title: "\LARGE"
\title{La vie au XXI\textsuperscript{e} siècle\[1\baselineskip]
\Large % or "\large" % switch to a smaller relative font size
La vie au XXI\textsuperscript{e} siècle} % subtitle
\author{Moi}
\date{\today}
\maketitle
\clearpage
% remainder of document
\end{document}
\subtitledirective, not the\superscriptdirective inside the argument of\subtitle, that causing the error message. (To verify this assertion, simply replace\subtitle{La vie au XXI\textsuperscript{e} si\ecle}with\subtitle{La vie au XXIe si`ecle}and recompile.) The basicbookdocument class does not define a macro called\subtitle. Do you maybe need to load a package in order to define\subtitle`? – Mico May 30 '21 at 08:09undefined control sequenceis due to\textsuperscript? As far as I remember, ther is no\subtitlein a regularbookclass, so I would suspect something like\subtitle{text}to result in the same error message. – leandriis May 30 '21 at 08:09bookdocument class. – Mico May 30 '21 at 08:46