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I think you can try like this

Mat im(50,50,CV_32FC2);
Point pt1(10,10),pt2(20,30);
for (int i = 0; i<im.rows; i++)
    for (int j = 0; j<im.cols; j++)
        im.at<Vec2f>(i,j) = Vec2f(i,j);
cv::LineIterator it(im, pt1, pt2, 8);
for (int i = 0; i < it.count; i++, ++it)
{
        cv::Point p = it.pos();
        Vec2f pixelValue = im.at<Vec2f>(p.y, p.x);
        cout<<pixelValue<<endl;
}

I think you can try like this

Mat im(50,50,CV_32FC2);
Point pt1(10,10),pt2(20,30);
for (int i = 0; i<im.rows; i++)
    for (int j = 0; j<im.cols; j++)
        im.at<Vec2f>(i,j) = Vec2f(i,j);
cv::LineIterator it(im, pt1, pt2, 8);
for (int i = 0; i < it.count; i++, ++it)
{
        cv::Point p = it.pos();
        Vec2f pixelValue = im.at<Vec2f>(p.y, p.x);
im.at<Vec2f>(p);
        cout<<pixelValue<<endl;
}

I think you can try like this

Mat im(50,50,CV_32FC2);
Point pt1(10,10),pt2(20,30);
for (int i = 0; i<im.rows; i++)
    for (int j = 0; j<im.cols; j++)
        im.at<Vec2f>(i,j) = Vec2f(i,j);
cv::LineIterator it(im, pt1, pt2, 8);
for (int i = 0; i < it.count; i++, ++it)
{
        cv::Point p = it.pos();
        Vec2f pixelValue = im.at<Vec2f>(p);
        cout<<pixelValue<<endl;
cout<<"pixel "<<p<<" = "<<pixelValue<<endl;
}