I have a very simple MWE which demonstrates the problem:
\documentclass{book}
\usepackage{graphicx}
\usepackage{subcaption}
\begin{document}
\begin{figure}
\centering
\begin{subfigure}[b]{0.20\linewidth}
\includegraphics[width=\linewidth]{example-image-a}
\caption{}\label{fig:1a}
\end{subfigure}%
\begin{subfigure}[b]{0.20\linewidth}
\includegraphics[width=\linewidth]{example-image-b}
\caption{}\label{fig:1b}
\end{subfigure}
\begin{subfigure}[b]{0.20\linewidth}
\includegraphics[width=\linewidth]{example-image-c}
\caption{}\label{fig:1b}
\end{subfigure}
\begin{subfigure}[b]{0.20\linewidth}
\includegraphics[width=\linewidth]{example-image-a}
\caption{}\label{fig:1b}
\end{subfigure}
\caption{A figure}\label{fig:1}
\end{figure}
\end{document}
Which outputs:

Why is there no spacing between A and B, but there is between B,C and A?

%percent sign after the first subfigure? This kills the space introduced by the linebreak. – Johannes_B Aug 18 '14 at 13:57